Abstract Gold catalysts are extensively utilized in photothermal processes that rely on localized surface plasmon resonance effects. However, the development of novel gold(I)‐organic frameworks that function as highly efficient photothermal catalysts for the production of hydrogen peroxide from water and oxygen presents a fascinating and challenging research opportunity. Herein, three gold(I) cyclic trinuclear complexes (Au‐CTCs) based metal–organic frameworks (MOFs) are prepared, exhibiting good photothermal conversion efficiency and H 2 O 2 evolution rates. Utilizing the optimized Au‐TFPT, the production rates of H₂O₂ can reach as high as 51,987 µ m g⁻¹ h⁻¹, surpassing the performance of most reported metal–organic frameworks (MOFs), even with the use of sacrificial agents to accelerate the reaction. The thermal‐assisted photocatalytic mechanism is comprehensively studied by transient photocurrent response, electrochemical impedance, electron paramagnetic resonance, rotating ring disk electrode test, catalytic performance and among others, demonstrating thermal energy can enhance the mobility of photogenerated carriers and apparent quantum yield, regulate the reactive species ratio and H 2 O 2 selectivity, reduce the apparent activation energy of photocatalysis, and improve mass transfer rates, thereby accelerating the reaction process. This study offers new insights into the thermal‐assisted photocatalytic production of H 2 O 2 .