The behavior of graphene-coated n-type Si(111) photoanodes was compared to the behavior of H-terminated n-type Si(111) photoanodes in contact with aqueous K-3[Fe(CN)(6)]/K-4[Fe(CN)(6)] as well as in contact with a series of outer-sphere, one-electron redox couples in nonaqueous electrolytes. The n-Si/Graphene electrodes exhibited stable short-circuit photocurrent densities of over 10 mA cm(-2) for >1000 s of continuous operation in aqueous electrolytes, whereas n-Si-H electrodes yielded a nearly complete decay of the current density within similar to 100 s. The values of the open-circuit photovoltages and the flat-band potentials of the Si were a function of both the Fermi level of the graphene and the electrochemical potential of the electrolyte solution, indicating that the n-Si/Graphene did not form a buried junction with respect to the solution contact.