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Photoelectrochemical (PEC) water splitting is a promising technology for solar hydrogen production to build a sustainable, renewable and clean energy economy. Given the complexity of the PEC water splitting processes, it is important to note that developing in-situ techniques for studying PEC water splitting presents a formidable challenge. This review is aimed at highlighting advantages and disadvantages of each technique, while offering a pathway of potentially combining several techniques to address different aspects of interfacial processes in PEC water splitting. We reviewed recent progress in various techniques and approaches utilized to study PEC water splitting, focusing on spec-troscopic and scanning-probe methods.