Solvent-modulated fluorescence behavior of select alternant and nonalternant polycyclic aromatic hydrocarbons (PAHs) dissolved inorganic nonelectrolyte solvents of varying polarity is reviewed. Theoretical models and practical examples of probe methods are given to illustrate determination of association constants for PAH-cyclodextrin guest-host inclusion complexes, and determination of preferential solvation around an excited-state fluorophore dissolved in a binary solvent mixture based upon measured emission intensities. Electron transfer mechanism (s) involving nitromethane and polycyclic aromatic hydrocarbons are critically evaluated in both organic nonelectrolyte and aqueous micellar surfactant (anionic, cationic, nonionic and zwitterionic) solvent media. Nitromethane is a known selective quenching agent for discriminating between alternant versus nonalternant polycyclic aromatic hydrocarbons. Fluorescence emission quenching selectivity is lost, however, in the case of anionic surfactants.