AbstractTraditional water–gas shift reaction provides one primary route for industrial production of clean-energy hydrogen. However, this process operates at high temperatures and pressures, and requires additional separation of H₂ from products containing CO₂, CH₄ and residual CO. Herein, we report a room-temperature electrochemical water–gas shift process for direct production of high purity hydrogen (over 99.99%) with a faradaic efficiency of approximately 100%. Through rational design of anode structure to facilitate CO diffusion and PtCu catalyst to optimize CO adsorption, the anodic onset potential is lowered to almost 0 volts versus the reversible hydrogen electrode at room temperature and atmospheric pressure. The optimized PtCu catalyst achieves a current density of 70.0 mA cm⁻² at 0.6 volts which is over 12 times that of commercial Pt/C (40 wt.%) catalyst, and remains stable for even more than 475 h. This study opens a new and promising route of producing high purity hydrogen.