Selective release of hydrogen from formic acid (FA) is deemed feasible to solve issues associated with the production and storage of hydrogen. Here, we present a new efficient photocatalytic system consisting of CdS nanorods (NRs), Ni, and Co to liberate hydrogen from FA. The optimized noble‐metal‐free catalytic system employs Ni/Co as a redox mediator to relay electrons and holes from CdS NRs to the Ni and Co, respectively, which also deters the oxidation of CdS NRs. As a result, a high hydrogen production activity of 32.6 mmol h⁻¹ g⁻¹ from the decomposition of FA was noted. Furthermore, the photocatalytic system exhibits sustained H₂ production rate for 12 h with sequential turnover numbers surpassing 4×10³, 3×10³, and 2×10³ for Co–Ni/CdS NRs, Ni/CdS NRs, and CoCl₂/CdS NRs, respectively.