The structures of several unstable or metastable reaction intermediates that were photoproduced in crystals were analyzed by using X-ray techniques. The presence of enough void space around the reactive group(s) is an essential factor for the reaction to occur with retention of the single-crystal form. To expand the void space, an acid group (COOH) was substituted onto the reactant molecule and acid-base complex crystals were prepared with several amines, such as dibenzylamine and dicyclohexylamine. Following the formation of such acid-base complexes in crystals, the metastable structures of nitrenes and red species of photochromic salicylideneanilines have been successfully analyzed by using X-ray techniques. Moreover, the structure of a Pt complex anion in the excited state has been analyzed, which formed acid-base complex crystals with various alkylammonium cations. The formation of acid-base complexes will be a powerful tool for directly observing the structure of unstable or metastable reaction intermediates by using X-ray techniques.