Photothermal catalysis has attracted great attention owing to high solar energy utilization efficiency, and great progress has been achieved in gas‐phase catalysis. However, photothermal catalysis in liquid‐phase shows a limited performance, due to high specific heat capacity of liquid. Herein, an interfacial photothermal catalytic (IPC) strategy applying an IPC leaf was designed for liquid‐phase catalysis using benzyl alcohol oxidation as the model reaction. On even ground, the benzaldehyde generation rate (8.7 mmol gcat−1 h−1) of the IPC system with Ce‐doped MnO2 as photothermal catalyst was almost 4.8 times and 3 times of bulk photothermal catalysis and the relative bulk thermal catalysis. Experimental results proved that this excellent catalytic performance could be attributed to both the high temperature achieved and the enhanced lattice oxygen activity by solar irradiation. This IPC system also exhibited good universality and long‐term durability. Our work innovatively created a green strategy to obtain fine chemicals with only solar irradiation.