The development and advancement of new materials for solar-driven chemistry is an area of focused attention because there remains no material that meets the demanding criteria for semiconductor solar photoelectrochemistry, which include stability, efficiency, and scalability. Modern techniques of materials discovery, such as high throughput synthesis and computational screening methods, have proved effective at identifying new classes of materials. However, these materials will require efficient and comprehensive characterization to expose their underlying physics, governed by their electronic structure and native defects. Through utilization of BiVO₄ as a testbed, we have developed a scalable synthetic method and a series of characterization tools to elucidate its underlying optical and electronic properties, as well as to mitigate photocarrier recombination at native defects and improve doping. These methods have since been applied to copper vanadate, an n-type semiconductor that has been newly identified as a candidate for use in photoelectrochemical energy conversion, to examine its apparent low performance efficiency.