Trajectory surface hopping simulations are performed to better understand the electronic relaxation dynamics of [Fe(bpy)3]2+ in aqueous solution. Specifically, the ultrafast relaxation from the photoexcited singlet metal-to-ligand charge-transfer (MLCT) to the metastable quintet metal-centered (MC) states is simulated through the surface hopping method, where the MLCT and MC states of [Fe(bpy)3]2+ in aqueous solution are computed by using a model electronic Hamiltonian developed previously. As a result, most of the trajectories are interpreted to show the sequential relaxation pathways via the triplet MC states, though some are the direct pathway from MLCT to the quintet MC states. Even though the triplet MC states are involved in the relaxation, the population transfer to the singlet MC ground state is very small, and the population of the quintet MC states reaches more than ∼96%, reasonably consistent with the unity quantum efficiency discussed experimentally.