The spectral-luminescent properties and photolysis of phenol and some of its derivatives have been considered experimentally and by methods of quantum chemistry. It has been shown that the substitution with a methyl group ( p -cresol) and the introduction of the second benzene ring (bisphenol A) lead to a shift of absorption bands toward longer wavelengths and some changes in their intensity. The non-planar structure of p -cresol and bisphenol A promotes an increase in the efficiency of singlet-triplet conversion and a decrease in the fluorescence quantum yield. Results of calculations have established the mechanisms of photolysis of the considered molecular systems. It has been shown that the O–H bond in phenol and p -cresol is broken by the pre-dissociation mechanism. Photolysis of bisphenol A upon exposure to solar radiation proceeds by the mechanism of direct dissociation, but with a noticeable potential barrier (~12000 cm –1 ).