Graphene quantum dots are known to exhibit tunable photoluminescence (PL) through manipulation of edge functionality under various synthesis conditions. Here, we report observation of excitation dependent anomalous m–n type fingerprint PL transition in synthesized amino functionalized graphene quantum dots (5–7 nm). The effect of band-to-band π*–π and interstate to band n–π induced transitions led to effective multicolor emission under changeable excitation wavelength in the functionalized system. A reasonable assertion that equi-coupling of π*–π and n–π transitions activated the heterogeneous dual mode cyan emission was made upon observation of the PL spectra. Furthermore, investigation of incremented dimensional scaling through facile synthesis of amino functionalized quantum graphene flakes (20–30 nm) revealed it had negligible effect on the modulated PL pattern. Moreover, an effort was made to trace the origin of excitation dependent tunable heterogeneous photoluminescence through the framework of energy band diagram hypothesis and first principles analysis. Ab initio results suggested formation of an interband state as a manifestation of p orbital hybridization between C–N atoms at the edge sites. Therefore comprehensive theoretical and experimental analysis revealed that newly created energy levels can exist as an interband within the energy gap in functionalized graphene quantum structures yielding excitation dependent tunable PL for optoelectronic applications.