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Converting solar energy into valuable hydrogen and hydrocarbon fuels through photocatalytic water splitting and CO2 photo-reduction is highly promising in addressing the growing demand for renewable and clean energy resources. Developing efficient photocatalysts for solar-driven H2 production and CO2 reduction is the most essential part in achieving this goal. For the purpose of attaining high photocatalytic efficiency, hetero-nanostructures formed by multiple material components have been demonstrated as an effective strategy. Within this heterostructure, its interface is a critical consideration, whereby it determines the principle of charge transfer across the heterojunctions and consequent surface reactions. This article reviews the recent developments of hetero-nanostructures for photocatalytic H2 production and CO2 reduction based on material compositions that form heterojunctions.