Single crystals of Re6Se7Br4 have been grown by chemical vapor transport. The photoelectrochemical characteristics of the compound have been investigated in aqueous electrolytes. Re6Se7Br4 behaves as a p-type semiconductor photoelectrode and exhibits considerable cathodic photocurrents in the visible region. Analysis of the spectral response indicates an indirect band gap of about 1.78 eV for the compound. Current-voltage measurements indicate that the electrode is unstable under applied potentials.