A family of solid solutions, Cu-5(Ta1-xNbx)(11)O-30 (0 <= x <= 0.4), was investigated as p-type semiconductors for their band gaps and energies and for their activity for the reduction of water to molecular hydrogen. Compositions from 0 to 40 mol % niobium were prepared in high purity by solid-state methods, accompanied by only very small increases in the lattice parameters of similar to 0.05% and with the niobium and tantalum cations disordered over the same atomic sites. However, an increasing niobium content causes a significant decrease in the bandgap size from similar to 2.58 to similar to 2.05 eV owing to the decreasing conduction band energies. Linear-sweep voltammetry showed an increase in cathodic photocurrents with niobium content and applied negative potential of up to -0.6 mA/cm(2) (pH similar to 7.3; AM 1.5 G light filter with an irradiation intensity of similar to 100 mW/cm(2)). The cathodic photocurrents could be partially stabilized by heating the polycrystalline films in air at 550 degrees C for 1 h to produce surface nanoislands of CuO or using protecting layers of aluminum-doped zinc oxide and titania. Aqueous suspensions of the Cu-5(Ta1-xNbx)(11)O-30 powders were also found to be active for hydrogen production under visible-light irradiation in a 20% aqueous methanol solution with the highest apparent quantum yields for the 10% and 20% Nb-substituted samples. Electronic structure calculations show that the increased photocurrents and hydroen evolution activities of the solid solutions arise near the percolation threshold of the niobate/tantalate framework wherein the Nb cations establish an extended O-Nb-O-Nb-O- diffusion pathway for the minority carriers. The latter also reveals a novel pathway for enhancing charge separation as a function of the niobium-oxide connectivity. Thus, these results illustrate the advantages of using solid solutions to achieve the smaller bandgap sizes and band energies that are needed for solar-driven photocatalytic reactions.