To study the possibility of photochromic transformations in the crystals of bifunctional compounds, quantum chemical B3LYP/6-31G(d) calculations of the Cspiro-O bond dissociation energies were carried out with the Gaussian-03 program for two dissimilar neutral spiropyrans (Sp) and three cations of their salts in the singlet ground state. For Cspiro-O bond dissociation in the cations Sp + and the neutral systems SpI consisting of Sp + and I−, the energy barriers do not exceed 10 kcal mol−1, increasing when moving from the cations Sp + to the neutral systems SpI. The changes in the HOMO and LUMO energies when going from the closed to open form of the cations Sp + correlate with the energy barriers to the corresponding Cspiro-O bond dissociations.