Infrared matrix isolation spectroscopy and DFT/B3LYP/6-311++G(d,p) calculations have been used to characterize the conformational space of the enol-imine and keto-amine tautomers of N-salicylidene-p-carboxyaniline (SCA) in both their E and Z isomeric forms. Monomers of SCA were isolated in an argon matrix (15 K), which was shown to contain only the most stable conformer of the E-enol isomer of the compound. The matrix-isolated E-enol was then subjected to in situ UV irradiation (λ = 335; 345 nm, provided by a laser/MOPO system, or λ > 235 nm, provided by a Hg(Xe) broad-band source), and the photoinduced processes probed by infrared spectroscopy. Two photoreaction channels were observed, with a branching ratio of ∼1:1, corresponding to E-enol → Z-enol isomerization and E-enol → E-keto tautomerization. Both processes were found to be rather effective, with practically complete consumption of the reactant after broad-band irradiation by 1 min only. Identification among the photoproduced species of the Z-enol conformer that differs from the reactant only by E-to-Z isomerization suggests the initial photoproduction of this conformer, which subsequently decays into the lowest energy Z-enol conformer (also identified experimentally). The E-enol → E-keto tautomerization requires an excited state intramolecular proton transfer and twisting about the exocyclic CC bond of the molecule. These processes most probably take place sequentially. However, in the present study the Z-keto isomer, which should act as intermediate in this sequence of processes, could not be detected, most probably due to its short lifetime under the used experimental conditions. On the contrary, the detailed structural and vibrational characterization of the photoproduced E-keto form was successfully achieved.