Recently, molecular photoswitches have garnered significant attention in the realm of research. The photochemistry of the azo (–N = N–) group due to its photodynamic features associated with the reversible (trans–cis-trans) isomerization cycle considers azo compounds as light-driven molecular devices. This research investigates the effect of mordant red and its derivatives as a photochromic molecule. The MRC1 and MRT1 showed valuable results among all. These derivatives are further explored with the graphene sheet. Density functional theory (DFT) computations were used to analyze the compounds’ and complexes’ structural and electrical characteristics. The garphene + MRC1 and graphene + MRT1 show 264,022.905 kJ/mol of change in energy which is much higher than the MRC1 and MRT1. These may show valuable results in effective photochromism. Furthermore, the interactions within the complexes were investigated through natural bond orbital (NBO) and noncovalent interactions (NCI) analysis. Moreover, the stability of the complexes was examined via molecular dynamics (MD) simulations using GROMACS. These were extensively and successfully employed in research on the structural and electrical characteristics of several azo-containing compounds. The research gives valuable results and might be useful for photoswitching molecules.