Chiral aryl 4-tolyl sulfoxides substituted with several sizes of aromatic rings, (S)-(-)-phenyl 4-tolyl sulfoxide (PHSO), (R)-(+)-1-naphthyl 4-tolyl sulfoxide (NASO), (R)-(+)-9-phenanthryl 4-tolyl sulfoxide (PNSO), and (R)-(+)-1-pyrenyl 4-tolyl sulfoxide (PYSO), were prepared. It has turned out for the first time that there are n–σ*, π–σ* and π–π* states in excited states of these molecules by MO calculation. Fluorescence spectra and quantum yields of fluorescence, Φfl, were measured in polar and non-polar solvents. Quantum yields of photoinversion, Φinv, and photolysis, Φdec, were also obtained with CD and HPLC measurements. Aromatic-ketone like characteristics have been noticed in the fluorescence measurements, i.e., fluorescence has been observed from sulfoxides substituted with large aromatic rings and their fluorescence becomes strong in a polar solvent. We attributed these characteristics to the decrease in π–π* transition energy as the degree of conjugation increases, while n–π* and π–σ* transition energy does not decrease so much. The values of Φinv and Φdec for PHSO, NASO and PNSO were found to be 0.3–0.4 (Φinv) and 0.03–0.05 (Φdec). The quantum yields for PYSO were measured as Φinv = 0.02–0.03 in methanol and hexane, and Φdec = 0.002–0.003 in methanol and 0.012–0.016 in hexane. It was found that quantum yields of photoinversion and photolysis decrease as the π–π* transition energy decreases. We concluded that photoinversion occur during change in electronic states from n–π* states to the ground state.