Although most fulgides show their photochromism in the solid state, crystal structure changes accompanying the photochromism have not been previously observed. The photochromic reactions have been so far considered to take place on surfaces or at defects of the crystals or to proceed with destruction of the crystals. In this study we have succeeded in observing crystal structure changes accompanying the photochromism of fulgides using X-ray diffraction analysis. Detection of the photoproducts in the crystal structures was not possible when the single crystals of the fulgides were irradiated with steady UV light. Two-photon excitation by pulsed laser light was essential to produce a sufficient amount of the photoproducts without significant deterioration in the quality of the crystals.