Diarylbenzopyrans and their annulated derivatives are a class of photochromic compounds, which have been extensively investigated for photochromism. In fact, some naphthopyrans are employed industrially in ophthalmic lens applications. Photoirradiation of 2,2-diphenylbenzopyran leads to the formation of coloredo-quinonoid intermediates. The latter revert too rapidly to allow their observation only at low temperatures (173–263 K). Annulation and other strategies are exploited to observe the colored o-quinonoid intermediates that persist for a few minutes at room temperature. We have examined photochromism of a set of silyloxysubstituted 2,2-diphenylbenzo- and naphthopyrans to explore how the mesomeric effects transmitted by the strongly e-donating silyloxy group substituted in the ring and at phenyl groups manifest in the spectrokineticproperties of their photogenerated colored o-quinonoid intermediates. We show that silyloxy substitution in the benzopyran ring leads to remarkable stabilization of the colored intermediates to enable their persistence at 283 K for a few minutes. In contrast, similar substitution in the C2-phenyl rings destabilizes the colored intermediates.