Novel mero/bis-mero cyanine dyes based on N-Bridgehead imidazo[1,2-g]quinolino[2,1-a][2,6]naphthyridine have been synthesized and characterized to evaluate intramolecular charge transfer (ICT) effect on the energy gap (E0-0). The UV–vis and emission spectral studies revealed that dyes are absorbed in the region of λmax 485–577 nm and emitted at 567–673 nm. Their solvatochromic behavior in solvents of various polarities, CCl4, C6H6, H2O, CHCl3, acetone, and DMF, was studied to emphasize the effect of solvent polarity on the absorption maxima, molar extinction coefficients of the dyes, and excitation energy of the dyes. Their electron cloud delocalization in HOMO/LUMO levels were studied by DFT using Gaussian 09 software. Time-dependent density functional theory (TD-DFT) was applied to theoretically explore the first excitation energy (E0-0) of these dyes, which was in good agreement with experimental results.