Atomically precise metal nanoclusters are featured by excellent physicochemical properties including quantum confinement effect, photosensitization capability and peculiar atomic stacking fashion, which are distinct from conventional metal nanocrystals. Thus far, investigation on the metal nanoclusters-involved photocatalysis and photoelectrocatalysis along with charge transfer characteristics has still been in the infant stage. To this end, we devote to crafting various novel metal nanoclusters-based heterostructures and evaluating their promising potential in photocatalysis and photoelectrocatalysis. Our work in this field would enrich the construction of diverse metal nanoclusters-based photocatalysts or photoelectrodes and provide new fundamental understanding on the charge transport features of metal nanoclusters for solar energy conversion.