The photochemistry of the hydrogen-bonded pyridine-water complex has been investigated with ab initio computational methods. Vertical excitation energies, excited-state reaction paths for proton transfer as well as structures and energies of conical intersections and reaction barriers have been determined with multi-configuration self-consistent-field and multi-reference perturbation methods, as well as with single-reference coupled-cluster and propagator methods. In the pyridine-water complex, the energies of two charge-separated excited states of (1)nπ* and (1)ππ* character are connected to the energies of the locally excited (1)nπ* and (1)ππ* states of the pyridine chromophore via a low energy barrier. The charge-separated excited states are strongly stabilized by the transfer of a proton from water to pyridine. The energies of the resulting biradical states intersect the potential-energy surface of the closed-shell ground state as a function of the proton-transfer coordinate. The resulting radical pair may dissociate to yield pyridinium and hydroxyl radicals. The photochemistry of the hypervalent pyridinium radical has been explored with the same computational methods. It has been found that a low-lying dissociative (2)πσ* excited state exists in pyridinium, which can lead to the photodetachment of the hydrogen atom. Overall, the H2O molecule can thus be dissociated into H˙ and OH˙ radicals by the absorption of two ultraviolet photons. The relevance of these results for solar water splitting and solar carbon dioxide reduction is discussed.