This contribution is an investigation of both the structures and optical properties of a set of 14 diverse, recently synthesized diarylethenes using Time-Dependent Density Functional Theory (TD-DFT) at the ωB97X-D/6-31G(d) level of theory. The linear response (LR) and state-specific (SS) versions of the Polarizable Continuum Model (PCM) have been adopted to account for the bulk solvation effects and their relative performances were critically accessed. It is shown, for the first time in the case of nontrivial diarylethenes, that TD-DFT provides good agreement between the experimental absorption-fluorescence crossing points (AFCPs) and their theoretical counterparts when a robust model accounting for both geometrical relaxation and vibrational corrections is used instead of the vertical approximation. On the other hand, the theoretical estimates for the Stokes shifts based on the vertical transition energies were found to be in disagreement with respect to experiment, prompting us to simulate the absorption/emission vibronic band shapes. It is proved that difficulties associated with the breakdown of the harmonic approximation in Cartesian coordinates exist for the investigated system, and we show how they can be at least partially overcome by means of a vertical approach including Duschinsky effects. Our results provide a valuable basis to rationalize the experimental vibronic structure of both emission and absorption bands and are expected to be a significant asset to the understanding of the optical properties of diarylethene derivatives.