Photo-/electrocatalysis serves as a cornerstone in addressing global energy shortages and environmental pollution, where the development of efficient and stable catalysts is essential yet challenging. Despite extensive efforts, it's still a formidable task to develop catalysts with excellent catalytic behaviours, stability, and low cost. Because of its high precision, favorable controllability and repeatability, radiation technology has emerged as a potent and versatile strategy for the synthesis and modification of nanomaterials. Through meticulous control of irradiation parameters, including energy, fluence and ion species, various inorganic photo-/electrocatalysts can be effectively synthesized with tailored properties. It also enables the efficient adjustment of physicochemical characteristics, such as heteroatom-doping, defect generation, heterostructure construction, micro/nanostructure control, and so on, all of which are beneficial for lowering reaction energy barriers and enhancing energy conversion efficiency. This review comprehensively outlines the principles governing radiation effects on inorganic catalysts, followed by an in-depth discussion of recent advancements in irradiation-enhanced catalysts for various photo-/electrocatalytic applications, such as hydrogen and oxygen evolution reactions, oxygen reduction reactions, and photocatalytic applications. Furthermore, the challenges associated with ionizing and non-ionizing radiation are discussed and potential avenues for future development are outlined. By summarizing and articulating these innovative strategies, we aim to inspire further development of sustainable energy and environmental solutions to drive a greener future.