Chiral pentenoates 1-3 in both Z and E isomeric forms underwent stationary irradiations in several solvents and in the presence of different photosensitizers. The photostationary-state ratio has been determined for each Z/E couple showing a predominance of the thermodynamically more stable isomer for 1 and 3. Moreover, transient species were generated by pulsed laser excitation and detected by their characteristic ultraviolet absorptions, being the first time that enoate-originated triplets are detected. Stern-Volmer quenching studies afforded a quantitative measure for the efficiency of the photosensitization processes induced by benzophenone or acetophenone and allowed the determination of the corresponding quenching rate constants. Density functional calculations permitted the determination of the geometries and the energies of the diastereomeric excited states. Two diastereomeric orthogonal and two diastereomeric planar structures result as a consequence of the presence of a chiral substituent. The orthogonal triplets are the energy minima in all cases, whereas the planar triplets are the transition states linking these orthogonal structures, the corresponding energy barriers being 8-10 kcal mol-1 for enoates 1-3. The computed S0 to T1 excitation energies show a trend which is consistent with the quenching rate constants. On the other hand, the triplet lifetimes determined for 1 and 2 are unusually long (1-20 μs) if compared with the data already described for several enones, in the range of nanoseconds. This fact has been rationalized from calculations of spin-orbit coupling at several points of the T1 potential energy surface. This coupling is maximum for structures with a torsional angle close to 45°, which are 4-5 kcal mol-1 above the minima of T1. Calculations done on the hypothetical aldehyde 4 and methyl vinyl ketone show much lower energy barriers, thus accounting for the shorter lifetimes reported for enone triplets.