Despite the importance of water photolysis in atmospheric chemistry, its mechanism is not well understood. Two different mechanisms for water photolysis have been proposed. The first mechanism is driven by water photoexcitation, followed by the reaction of the active hydrogen radical with water clusters. The second mechanism is governed by the ionization process. Both photoexcited and photoionized mechanisms are complementary, which is elucidated by using excited-state ab initio molecular dynamics simulations based on complete active space self-consistent field approach and unrestricted Moller-Plesset second-order perturbation theory based Born-Oppenheimer molecular dynamics simulations.