Surface-hopping dynamics coupled to linear response TDDFT and explicit nonadiabatic and spin–orbit couplings have been used to model the ultrafast intersystem crossing (ISC) dynamics in [Ru(bpy)₃]²⁺. Simulations using an ensemble of trajectories starting from the singlet metal-to-ligand charge transfer (¹MLCT) band show that the manifold of ³MLCT triplet states is first populated from high-lying singlet states within 26 ± 3 fs. ISC competes with an intricate internal conversion relaxation process within the singlet manifold to the lowest singlet state. Normal-mode analysis and principal component analysis, combined with further dynamical simulations where the nuclei are frozen, unequivocally demonstrate that it is not only the high density of states and the large spin–orbit couplings of the system that promote ISC. Instead, geometrical relaxation involving the nitrogen atoms is required to allow for state mixing and efficient triplet population transfer.