The spirooxazine/merocyanine couple constitutes a photochromic system that can change from the colorless spirooxazine to the intensely colored merocyanine by thermal or photochemical activation by a reaction that opens the spiro ring of the oxazine. The mechanisms of the ring-opening/closure reactions that interconnect these two isomers have been elucidated by means of a computational study. First, we have used the CASSCF/CASPT2 method to determine in detail these mechanisms in the gas phase for a small model that contains the photoactive part of the whole system. We have found that the state of spirooxazine excited by the initial absorption changes gradually to a lower excited state that is involved in a conical intersection that connects it with the ground state of merocyanine. The same conical intersection is involved in the backward photochemical reaction. Second, using a larger model that includes all the heteroatoms of the system and using the DFT (B3LYP) method, we have studied the influence of a solvent environment on the thermal equilibrium between the open and the closed species. It has been observed experimentally that the thermal equilibrium between these forms is practically unaltered by polar aprotic solvents, but it can be displaced toward the colored form in mixtures of polar protic and aprotic solvents, even if the first one is found in a very small proportion. To reproduce the experimental environments, we have taken into account the long-range effect of the polar aprotic solvent considering it a polarizable continuum, as done in the PCM method, and the short-range effect of the protic solvent including some explicit water molecules in the cluster studied at the atomic level. The results obtained are in good agreement with the experimental observations and explain the reason for this peculiar behavior.