A sustainable future demands innovative breakthroughs in science and technology today, especially in the energy sector. Earth-abundant resources can be explored and used to develop renewable and sustainable resources of energy to meet the ever-increasing global energy demand. Efficient solar-powered conversion systems exploiting inexpensive and robust catalytic materials for the photo- and photo-electro-catalytic water splitting, photovoltaic cells, fuel cells, and usage of waste products (such as CO ) as chemical fuels are appealing solutions. Many electrocatalysts and nanomaterials have been extensively studied in this regard. Low overpotentials, catalytic stability, and accessibility remain major challenges. Metal nanoclusters (NCs, ≤3 nm) with dimensions between molecule and nanoparticles (NPs) are innovative materials in catalysis. They behave like a "superatom" with exciting size- and facet-dependent properties and dynamic intrinsic characteristics. Being an emerging field in recent scientific endeavors, metal NCs are believed to replace the natural photosystem II for the generation of green electrons in a viable way to facilitate the challenging catalytic processes in energy-conversion schemes. This Review aims to discuss metal NCs in terms of their unique physicochemical properties, possible synthetic approaches by wet chemistry, and various applications (mostly recent advances in the electrochemical and photo-electrochemical water splitting cycle and the oxygen reduction reaction in fuel cells). Moreover, the significant role that MNCs play in dye-sensitized solar cells and nanoarrays as a light-harvesting antenna, the electrochemical reduction of CO into fuels, and concluding remarks about the present and future perspectives of MNCs in the frontiers of surface science are also critically reviewed.