Chirality is a fundamental property in nature, essential for the existence and survival of living organisms. Smart responsive chiroptical materials have attracted increasing attention due to their unique structural characteristics and potential applications. Azobenzene (Azo), a typical photoresponsive chromophore, plays a crucial role in constructing and controlling chiral structures. The unique cis-trans isomerization, liquid crystallinity, and other physicochemical properties allow for a wide range of tunability in stimuli-responsive chiroptical materials. This review summarizes recent research on chiral/achiral Azo building blocks for multilevel chiral generation and chiral switching, and discusses the applications of chiral Azo structures from micro to macro levels. It aims to provide an overview of potential challenges and new research opportunities for the development of novel smart responsive chiroptical materials. Azobenzene has two phenyl rings connected by a -N=N- group, and the degree of conjugation can alter its maximum absorption in the UV-visible light absorption spectrum. Azo molecules are widely used in functional dyes, additives, or colorants due to their efficient, reversible, and controllable cis-trans isomerization. The Azo unit generally exists in two isomeric forms: the thermodynamically stable trans-isomer and the less stable cis-isomer, which differ significantly in molecular polarity, size, shape, stability, and hydrophobicity. The cis-isomer has a bent structure with a reduced molecular size and an increased dipole moment. The isomerization between cis- and trans-configuration can be interconverted between UV and visible light irradiation or by heating treatment. Altering the substituents on Azo chromophore can modulate the photoresponse wavelength and significantly affect the half-life of the cis-isomer. The unique properties of Azo chromophore, such as liquid crystalline, photoalignment, reducibility, and guest responsiveness, offer vast potential in fields such as molecular switches and machines, surface modification, LC materials, responsive actuators, drug delivery, shape memory, and data storage. The regulation of helical superstructures and the controllable expression of chirality constitute a challenging task. Many ways to dynamically regulate the chiral helical structure, including temperature, light, solvent, magnetic field, and pH, have been explored. The unique properties of Azo units can be used to achieve the construction of chiral structures and the precise remote control of chirality. The construction and regulation of Azo-containing chiral structures involve the use of chiral molecules or assembled superhelical structures. The basic principle is to combine chiral molecules with stimulus-responsive groups by introducing chiral elements into the stimulus-responsive groups, and constructing chiral structures through chirality transfer and asymmetric amplification. The construction of individual chiral photoswitches holds great promise in the realm of smart-responsive materials. The review summarizes the recent progress of chiral generationChirality is a fundamental property in nature, essential for the existence and survival of living organisms. Smart responsive chiroptical materials have attracted increasing attention due to their unique structural characteristics and potential applications. Azobenzene (Azo), a typical photoresponsive chromophore, plays a crucial role in constructing and controlling chiral structures. The unique cis-trans isomerization, liquid crystallinity, and other physicochemical properties allow for a wide range of tunability in stimuli-responsive chiroptical materials. This review summarizes recent research on chiral/achiral Azo building blocks for multilevel chiral generation and chiral switching, and discusses the applications of chiral Azo structures from micro to macro levels. It aims to provide an overview of potential challenges and new research opportunities for the development of novel smart responsive chiroptical materials. Azobenzene has two phenyl rings connected by a -N=N- group, and the degree of conjugation can alter its maximum absorption in the UV-visible light absorption spectrum. Azo molecules are widely used in functional dyes, additives, or colorants due to their efficient, reversible, and controllable cis-trans isomerization. The Azo unit generally exists in two isomeric forms: the thermodynamically stable trans-isomer and the less stable cis-isomer, which differ significantly in molecular polarity, size, shape, stability, and hydrophobicity. The cis-isomer has a bent structure with a reduced molecular size and an increased dipole moment. The isomerization between cis- and trans-configuration can be interconverted between UV and visible light irradiation or by heating treatment. Altering the substituents on Azo chromophore can modulate the photoresponse wavelength and significantly affect the half-life of the cis-isomer. The unique properties of Azo chromophore, such as liquid crystalline, photoalignment, reducibility, and guest responsiveness, offer vast potential in fields such as molecular switches and machines, surface modification, LC materials, responsive actuators, drug delivery, shape memory, and data storage. The regulation of helical superstructures and the controllable expression of chirality constitute a challenging task. Many ways to dynamically regulate the chiral helical structure, including temperature, light, solvent, magnetic field, and pH, have been explored. The unique properties of Azo units can be used to achieve the construction of chiral structures and the precise remote control of chirality. The construction and regulation of Azo-containing chiral structures involve the use of chiral molecules or assembled superhelical structures. The basic principle is to combine chiral molecules with stimulus-responsive groups by introducing chiral elements into the stimulus-responsive groups, and constructing chiral structures through chirality transfer and asymmetric amplification. The construction of individual chiral photoswitches holds great promise in the realm of smart-responsive materials. The review summarizes the recent progress of chiral generation