The activation of water molecules in thermal catalysis typically requires high temperatures, representing an obstacle to catalyst development for the low‐temperature water‐gas shift reaction (WGSR). Plasmonic photocatalysis allows activation of water at low temperatures through the generation of light‐induced hot electrons. Herein, we report a layered double hydroxide‐derived copper catalyst (LD‐Cu) with outstanding performance for the low‐temperature photo‐driven WGSR. LD‐Cu offered a lower activation energy for WGSR to H2 under UV/Vis irradiation (1.4 W cm−2) compared to under dark conditions. Detailed experimental studies revealed that highly dispersed Cu nanoparticles created an abundance of hot electrons during light absorption, which promoted *H2O dissociation and *H combination via a carboxyl pathway, leading to the efficient production of H2. Results demonstrate the benefits of exploiting plasmonic phenomena in the development of photo‐driven low‐temperature WGSR catalysts.