Solar‐driven Fischer–Tropsch synthesis (FTS) holds great potential for the sustainable production of fuels from syngas and solar energy. However, the selectivity toward multi‐carbon products (C2+) is often hampered by the difficulty in the regulation of transition metals acting as both light absorption units and active sites. Herein, a partial phosphidation strategy to prepare titania supported Ni2P/Ni catalysts for photothermal FTS is demonstrated. Under Xenon lamp or concentrated sunlight irradiation, the optimized catalyst shows a C2+ selectivity of 70% at a CO conversion of >20%. Conversely, nickel metal in the absence of Ni2P delivers negligible C2+ products (≈1%) with methane being the major product (>90%). Structural characterization and density functional theory calculation reveal that the partial phosphidation allows exposed metallic Ni to be active for CO adsorption and activation, while the existence of Ni2P/Ni interface is responsible to inhibit CO methanation and promote C–C coupling of adsorbed *CH intermediates. This work introduces a novel phosphidation strategy for nickel‐based photothermal catalysts in efficiently harnessing solar energy, and regulating the reaction pathways for CO hydrogenation to deliver high value products.