Formic acid (HCOOH) has attracted much attention as a promising power source for portable electronic devices because of its ease of storage and transportation. Here we report that a simple HCOOH photo‐fuel cell (PFC) consisting of mesoporous anatase TiO2 photoanode and Pt cathode stably delivers a short‐circuit photocurrent (Jsc) of 5.94 mA cm−2 and an open‐circuit voltage of 0.94 V under UV‐light irradiation (light intensity, I = 200 mW cm−2). The incident photon‐to‐current conversion efficiency and Faradaic efficiency reach ~90% and ~100%, respectively. The excellent performances of this HCOOH PFC, designed based on the discovery that HCOOH provides a large photocurrent by current doubling even in the presence of O2, not only solves the problem of conventional HCOOH FCs, but also achieves the performances far exceeding those of PFCs using biomass‐derived organics reported so far.