We demonstrate that photochromism based on light-driven reversible C−N single bond cleavage can enable rapid coloration upon UV light irradiation and successive fast thermal back-reaction within tens of microseconds at room temperature. According to Marcus theory, the thermal back-reaction would be accelerated with increasing ΔG0, which is closely linked to the decrease in ΔG‡. We have considered that the ΔG0 of the thermal back-reaction could be enlarged by destabilizing the colored species and designed pseudogem-DPI-PI[2.2]PC, with a [2.2]paracyclophane moiety that couples diphenylimidazole and phenanthroimidazole groups. The present study demonstrates that controlling the stability of the biradical state is effective in accelerating the thermal back-reaction for the photochromic [2.2]paracyclophane-bridged imidazole dimer.