A mechanistic study of the intramolecular S → O linkage photoisomerization in the cis and trans isomers of [Ru(bpy)2(DMSO)2](2+) was performed using density functional theory. This study reveals that for the cis isomer the linkage photoisomerization of the two DMSO ligands occurs sequentially in the lowest triplet excited state and can either be achieved by a one-photon or by a two-photon mechanism. A mechanistic picture of the S → O photoisomerization of the trans isomer is also proposed. This work especially highlights that both adiabatic and nonadiabatic processes are involved in these mechanisms and that their coexistence is responsible for the rich photophysics and photochemical properties observed experimentally for the studied complexes. The different luminescent behavior experimentally observed at low temperature between the cis and trans isomers is rationalized based on the peculiarity of the topology of the triplet excited-state potential energy surfaces.