The water soluble molecular complex [Co(cyclam)(ClO4)]ClO4 (cyclam = 1,4,8,11-tetraazacyclotetradecane) is utilized as a precursor for deposition of highly active cobalt based nanostructured material on the electrode surface upon electrooxidation. The electrolysis of the complex at +1.1 V vs Ag/AgCl in 0.1 M potassium phosphate at pH 12 leads to the formation of a nanoporous Co(II) hydroxide/phosphate thin film on the printed carbon electrode. The deposited surface was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), and X-ray photoelectron spectroscopy (XPS). The modified electrode (Co-PCE-12) is stable for more than 34 h during the continuous electrolysis. The modified electrode exhibits a high water oxidation catalytic activity of 6.5 mA cm(-2) at an overpotential of 580 mV (0.9 V vs Ag/AgCl (3 M KCl) at pH 12) with 98% Faradaic yield. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.