A combined matrix isolation FTIR and theoretical DFT( B3LYP)/6-311++G( d, p) study of the photochemistry of sulfur analogues of alpha-pyrone [ 2H-thiopyran-2-one ( TP) and 2H-pyran-2-thione ( PT)] was carried out. The vibrational spectra of monomers of the compounds isolated in low-temperature argon matrixes were studied experimentally and assigned completely on the basis of theoretical calculations. UV irradiation ( lambda > 337 nm) of the studied compounds isolated in low-temperature matrixes results mainly in the ring-opening reaction by means of the cleavage of the alpha-bond. Other photoprocesses, not involving the alpha-bond-cleavage step ( such as generation of Dewar valence isomer), correspond to the minor reaction channels in both studied compounds. The ring-opening photoreaction in PT represents the first reported case of an alpha-bond cleavage in a compound with a CdS group attached to a six-membered ring, in which the internal strain practically does not exist, whereas the corresponding reaction in TP ( a cleavage of a C-S bond in the alpha position with respect to a carbonyl group) is now reported for the first time. Following the ring-opening reactions, isomerization processes and intramolecular hydrogen shift reactions were observed, enabling production of TP from PT and vice versa. A detailed study of such processes was undertaken, and kinetical and mechanistical data are presented and discussed.