Eumelanin is a polymeric structure made of dihydroxyindole (DHI) as the basic motif. Since the oxidative polymerization of DHI forms the core of eumelanin, understanding the effect of polymerization on its optical and photoprotective properties is crucial to elucidate the structure-function relationship of eumelanin. In this work, we investigate the effect of dimerization of DHI on the photoprocesses of eumelanin. We observe that there are several low-energy conical intersections and energetically favorable pathways for deactivation of photoexcited dimeric DHI species. While the original deactivation modes of the monomers are still important, in dimers the intermonomer dihedral angles seem to play a central role.