Gaussian-3 (G3) calculations have been carried out to examine the photodissociation of propylene sulfide at 193 nm. On the basis of the good agreements between the G3 results and experimental measurements, three dissociation channels involving transition structures have been established. The sulfur-containing products of these three dissociation reactions are C2H3S, HS, and H2S. Moreover, two channels leading to the loss of sulfur atom are observed experimentally and confirmed computationally. Furthermore, some additional elimination processes, also leading to the neutral fragments C3H6 and S(D-1) or S(P-3), and having exceedingly high experimental reaction barriers, are observed. These reactions are not likely to take place at the ground state of propylene sulfide. The experimentally measured high reaction barriers are in very good accord with our calculated excitation energies of propylene sulfide.