A high-throughput method has been developed using a commercial piezoelectric inkjet printer for synthesis and characterization of mixed-metal oxide photoelectrode materials for water splitting. The printer was used to deposit metal nitrate solutions onto a conductive glass substrate. The deposited metal nitrate solutions were then pyrolyzed to yield mixed-metal oxides that contained up to eight distinct metals. The stoichiometry of the metal oxides was controlled quantitatively, allowing for the creation of vast libraries of novel materials. Automated methods were developed to measure the open-circuit potentials (E_oc), short-circuit photocurrent densities (J_sc), and current density vs. applied potential (J–E) behavior under visible light irradiation. The high-throughput measurement of E_oc is particularly significant because open-circuit potential measurements allow the interfacial energetics to be probed regardless of whether the band edges of the materials of concern are above, close to, or below the values needed to sustain water electrolysis under standard conditions. The E_oc measurements allow high-throughput compilation of a suite of data that can be associated with the composition of the various materials in the library, to thereby aid in the development of additional screens and to form a basis for development of theoretical guidance in the prediction of additional potentially promising photoelectrode compositions.