The structure and electronic properties of the biphotochromic dyad with two styrylbenzo[f]quinoline photochromes, as well as the corresponding cyclobutane with two benzo[f]quinoline (BQ) substituents, are studied by DFT at the M06‐2X/6‐31G* level, the cyclobutane being a product of the [2 + 2] photocycloaddition (PCA) reaction of the dyad. According to calculations, the dyad forms π‐stacked folded conformers, which, when excited, can form excimers that are precursors of cyclobutane. TD DFT calculations and natural transition orbital (NTO) analysis indicated that the lowest singlet excited S1 state in the dyad is localized on the SBQ photochrome, including the ethylene group that undergoes PCA. Thus, the conditions for concerted electrocyclic reactions are satisfied, and the direct PCA follows the Woodward–Hoffmann rules. In contrast, in cyclobutane, the S1 state is localized on the BQ substituent rather than on the cyclobutane core. Therefore, the reverse ring‐opening (retro‐PCA) reaction cannot follow the Woodward‐Hoffmann rules and inevitably involves a step of excitation energy transfer from BQ to cyclobutane, which means the predissociation mechanism.