Crystal violet lactone (CVL) emits in aprotic solvents at room temperature single (A band, low polar solvents) or dual (A and B bands, medium and highly polar solvents) fluorescence. Strong solvatochromic shifts of both fluorescence bands prove significant charge redistribution in both emitting states ((CTA)-C-1 and (CTB)-C-1). Comparison with model compounds mimicking structural subunits of CVL, 6-dimethylaminophthalide (6-DMAPd), and malachite green lactone (MGL) shows that the A band is displayed from a polar excited state localized within the 6-DMAPd subunit ((CTA)-C-1, mu(e) similar or equal to 10.7 D), and the B band, from a highly polar excited state ((CTB)-C-1, mu(e) similar or equal to 25.2 D) formed after electron transfer from one of the dimethylaniline groups to 6-DMAPd moiety. The (CTB)-C-1 state becomes accessible and is populated during solvation by a sufficiently polar environment. CVL phosphorescence strictly matches that of 6-DMAPd, indicating ISC to a triplet state localized on 6-DMAPd moiety in low polar solvents. In polar solvents, transient absorption measurements indicate spin flip and relaxation to a charge-transfer triplet state, as evidenced by identical S-1 --> S-n and T-1 --> T-n spectra in acetonitrile indicating presence of dimethylaniline cation radical. In protic media, CVL undergoes fast photodissociation of the C-O bond in lactone ring and diabatic formation of a zwitterion stabilized by hydrogen bonding with solvent molecule.