Graphene oxide (GO) and its modified derivatives are widely studied because of their adjustable electronic and optical characteristics. In the present work, density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were employed to examine the influence of amination and alkali metal incorporation on GO-based systems. Aminated graphene oxide (fGO) together with Li, Na, and K containing mono- and co-doped derivatives were investigated through thermodynamic, electronic, optical, and interaction analyses. The calculated results reveal that functionalization and metal incorporation decrease the HOMO-LUMO energy gap and alter charge distribution, dipole moment, and global reactivity descriptors. UV–visible and transition density matrix analyses suggest improved charge delocalization and optical response after metal incorporation. Molecular dynamics simulations also confirm the structural stability and interaction behavior of selected systems. Overall, this theoretical investigation provides useful insight into tuning the electronic and optical properties of graphene oxide-based functional materials.