Tenorite CuO thin films have been synthesized via spray pyrolysis of aqueous copper(II) chloride solution followed by heat-treatment, exhibited a photocurrent density of 24 mA cm(-2) at 0.25 V vs. RHE under AM1.5G solar irradiation in alkaline electrolyte. This large photocurrent density has been attributed to a drift assisted transport of photo-generated electrons across the semiconductor/electrolyte interface in the annealed films. The tendency of photo-corrosion from the surface of CuO has been reduced substantially without any extra protective layer, simply by adding K3Fe(CN)(6) in the electrolyte, which acts as a sacrificial excess-electron scavenging agent. The fabricated electrode exhibited a positive onset potential at 0.25 V vs. RHE even after the electrolyte modification and a stable photocurrent density of more than 40% has been retained after 20 minutes of continuous illumination. The processed photocathode showed a solar to chemical conversion efficiency of 7.85% and 21.5% with and without using an electron scavenging agent, respectively. It holds the promise of using this photocathode in PEC energy conversion, photocatalysis and solar water splitting. (C) 2016 The Electrochemical Society. All rights reserved.