Among the vast array of transition metal complexes which have been previously reported, organometallic compounds based on iridium(III) and relevant metal complexes have been shown to possess particularly interesting features; including a wide range of versatile chemical structures, unique photophysical properties and, perhaps most importantly, outstanding photocatalytic capabilities. This review surveys the design and evaluation of these compounds as photocatalysts/photosensitizers in systems for photocatalytic hydrogen evolution (PHE) reactions. Photo-redox mechanisms are addressed, and structure-catalytic activity relationships are identified to guide the future design of more efficient and robust photocatalytic systems.