Raman spectroscopy is a powerful tool for characterizing the chemical and physical properties of graphene-based materials, both in laboratory and mass production settings. This review systematically discusses the developments in Raman spectroscopy of graphene-based materials from fundamental research and practical device applications perspectives. It describes the essential Raman scattering processes of the first- and second-order modes in intrinsic graphene, and discusses the shear, layer-breathing, G, and 2D modes of multilayer graphene with different stacking orders. Techniques to determine the number of graphene layers, probe resonance Raman spectra of monolayer and multilayer graphene, and obtain Raman images of graphene-based materials are also presented. The extensive capabilities of Raman spectroscopy for investigating the fundamental properties of graphene under external perturbations are described, which have also been extended to other graphene-based materials, such as graphene quantum dots, carbon dots, graphene oxide, nanoribbons, chemical vapor deposition-grown and SiC epitaxially grown graphene flakes, composites, and graphene-based van der Waals heterostructures. These fundamental properties have been used to probe the states, effects, and mechanisms of graphene materials present in the related heterostructures and devices. The review also covers the Raman spectroscopy of monolayer and multilayer graphene, including their electronic band structures, phonon dispersion, and Raman spectra. It discusses the principle of double and triple resonance Raman scattering in graphene, and how Raman spectroscopy can be used to identify the number of layers of graphene materials. The review also presents examples of the applications of Raman spectroscopy to graphene-related materials and devices, including graphene oxide, nanographene, epitaxial graphene grown from SiC, CVD-grown graphene, graphene-based heterostructures, field effect transistors (FETs), ion batteries, and solar cells. The application of Raman imaging is also presented in detail. This review aims to provide a comprehensive guide for anyone interested in the use of Raman spectroscopy with graphene-related systems and would like to employ Raman spectroscopy to characterize graphene-related materials and related devices.Raman spectroscopy is a powerful tool for characterizing the chemical and physical properties of graphene-based materials, both in laboratory and mass production settings. This review systematically discusses the developments in Raman spectroscopy of graphene-based materials from fundamental research and practical device applications perspectives. It describes the essential Raman scattering processes of the first- and second-order modes in intrinsic graphene, and discusses the shear, layer-breathing, G, and 2D modes of multilayer graphene with different stacking orders. Techniques to determine the number of graphene layers, probe resonance Raman spectra of monolayer and multilayer graphene, and obtain Raman images of graphene-based materials are also presented. The extensive capabilities of Raman spectroscopy for investigating the fundamental properties of graphene under external perturbations are described, which have also been extended to other graphene-based materials, such as graphene quantum dots, carbon dots, graphene oxide, nanoribbons, chemical vapor deposition-grown and SiC epitaxially grown graphene flakes, composites, and graphene-based van der Waals heterostructures. These fundamental properties have been used to probe the states, effects, and mechanisms of graphene materials present in the related heterostructures and devices. The review also covers the Raman spectroscopy of monolayer and multilayer graphene, including their electronic band structures, phonon dispersion, and Raman spectra. It discusses the principle of double and triple resonance Raman scattering in graphene, and how Raman spectroscopy can be used to identify the number of layers of graphene materials. The review also presents examples of the applications of Raman spectroscopy to graphene-related materials and devices, including graphene oxide, nanographene, epitaxial graphene grown from SiC, CVD-grown graphene, graphene-based heterostructures, field effect transistors (FETs), ion batteries, and solar cells. The application of Raman imaging is also presented in detail. This review aims to provide a comprehensive guide for anyone interested in the use of Raman spectroscopy with graphene-related systems and would like to employ Raman spectroscopy to characterize graphene-related materials and related devices.