Photochromism of p-methylthiobenzoylacetone (1) has been studied in argon and xenon cryogenic matrices. Application of linearly polarized light to induce the phototransformation resulted in partial alignment of both the initial structure and the photochromic product. Different orientations were achieved by using irradiation wavelengths corresponding to differently polarized electronic transitions. This was followed by measurements of linear dichroism (LD) in the IR region. The analysis of the IR spectra, combined with the results of DFT B3LYP/cc-pVDZ calculations enabled determining the structures of the most stable ground state species and of the photoproduct. Similarly to the recently reported cases of thioacetylacetone and monothiodibenzoylmethane, the initial structure of 1 corresponds to an intramolecularly hydrogen-bonded enol form, and the photochromic species to an “open”, nonchelated enethiolic form. Vibrational assignments have been made for both species, greatly helped by the analysis of the LD spectra. It is concluded that DFT calculations for 1 quite reliably predict not only vibrational frequencies and intensities, but also transition moment directions, in both IR and electronic spectra.