The ability to tune the microstructures, bandgap, conductance, chemical environment and thermal storage of carbon nanomaterials such as carbon nanotubes, graphene and fullerenes by optical modulation or response is important to design and fabricate advanced optoelectronic nanodevices. This review is focused on optical control and regulation of structures, properties, interface and interaction of a new generation of photo-responsive carbon nanomaterials/azobenzene moieties (Carbon–AZO) hybrids. The optical switching properties of Carbon–AZO hybrids resulting from the photo-isomerization between trans and cis isomers are highlighted and discussed in terms of photo-energy conversion devices including switches, sensors, detectors, fuels and storage. A wide range of advanced energy conversion devices using Carbon–AZO hybrids can be developed in the future by the optimization of the chemical structure, steric conformation, electrostatic environment and functionalization of specific molecules.