Chrysenes, picene, fulminene, modified with imide, bromo, and amino functionalities, were synthesized through Mallory photoreaction as the key step, and their electronic spectra were investigated. Fluorescence spectra of chrysene-diimide CHRDI and bromo-substituted phencanene-imides, BrCHRI, BrPICI, BrFULI were dependent on solvent polarity to display appreciable fluorescence color changes. The solvatofluorochromic behavior was analyzed by conventional relationships between Stokes shift and solvent polarity parameters, such as Lippert-Mataga and Bilot-Kawski equations. The results indicated that the solvatofluorochromism was derived from the intramolecular charge transfer (ICT) nature in the excited state. Theoretical studies using time-dependent density-functional theory revealed that the phenacene-imide molecules in the fluorescent state possessed ICT characters between the strongly electron-withdrawing imide moiety and moderately electron-donating phenacene cores. Amino-substituted chrysene-imide NH2CHRI showed fluorescence band in a red region (λFL = 618 nm) in toluene with a very large Stokes shift (Δν∼ = 7630 cm−1) suggesting that the molecule in the fluorescent state was highly polarized. The present results indicate that phenacenes would provide potential platforms for constructing future functional fluorophores through an appropriate functionalization.