This study reports the formation of chiral liquid crystals (CLCs) in aqueous graphene oxide (GO) dispersions and their subsequent use to create macroscopic, continuous graphene fibres. GO sheets, which are single-layered and highly dispersible in water, form CLCs through a twist-grain-boundary (TGB) phase-like model, exhibiting both lamellar and helical structures. These CLCs can be spun into metres of macroscopic GO fibres, which are then chemically reduced to produce neat graphene fibres with high electrical conductivity and mechanical strength. The resulting fibres can be woven into textiles and patterns, demonstrating their potential for various applications. The research highlights the unique properties of GO and its ability to form CLCs, which are significant for understanding colloid physics and enabling fluid-phase assembly. The GO CLCs exhibit strong circular dichroism (CD) activity, indicating a helical arrangement of GO sheets. The study also demonstrates that the helical structure of GO CLCs is influenced by electrostatic repulsion between GO sheets, which plays a key role in their formation. The study further shows that GO CLCs can be used as templates to create chiral porous materials and silica-based chiral gel films. Additionally, the wet-spinning technique used to produce GO and graphene fibres is industrially viable and allows for the fabrication of high-performance carbon fibres from natural graphite. The resulting fibres have excellent mechanical properties, high electrical conductivity, and flexibility, making them suitable for applications in textiles, sensors, and other fields. The research provides a new method for fabricating high-performance carbonaceous fibres with versatile functionalities from natural graphite. The findings contribute to the understanding of 2D colloidal systems and open new avenues for the development of advanced materials.This study reports the formation of chiral liquid crystals (CLCs) in aqueous graphene oxide (GO) dispersions and their subsequent use to create macroscopic, continuous graphene fibres. GO sheets, which are single-layered and highly dispersible in water, form CLCs through a twist-grain-boundary (TGB) phase-like model, exhibiting both lamellar and helical structures. These CLCs can be spun into metres of macroscopic GO fibres, which are then chemically reduced to produce neat graphene fibres with high electrical conductivity and mechanical strength. The resulting fibres can be woven into textiles and patterns, demonstrating their potential for various applications. The research highlights the unique properties of GO and its ability to form CLCs, which are significant for understanding colloid physics and enabling fluid-phase assembly. The GO CLCs exhibit strong circular dichroism (CD) activity, indicating a helical arrangement of GO sheets. The study also demonstrates that the helical structure of GO CLCs is influenced by electrostatic repulsion between GO sheets, which plays a key role in their formation. The study further shows that GO CLCs can be used as templates to create chiral porous materials and silica-based chiral gel films. Additionally, the wet-spinning technique used to produce GO and graphene fibres is industrially viable and allows for the fabrication of high-performance carbon fibres from natural graphite. The resulting fibres have excellent mechanical properties, high electrical conductivity, and flexibility, making them suitable for applications in textiles, sensors, and other fields. The research provides a new method for fabricating high-performance carbonaceous fibres with versatile functionalities from natural graphite. The findings contribute to the understanding of 2D colloidal systems and open new avenues for the development of advanced materials.