Coatings were deposited on graphite and titanium from an aqueous solution based on a water‐soluble precursor. A two‐step mechanism is suggested for the formation: generation of hydroxyl ions (OH−) at the cathodic substrate by reduction of and dissolved , and then reaction of the hydroxyl ions with zirconyl ions present in the solution to form the hydroxide , which in turn decomposes on drying to yield zirconia . Faradaic efficiencies of 20–50% were found, attributable to reduction reactions that do not produce hydroxyl ions, as well as to formation of the hydroxide at sites removed from the cathodic substrate due to diffusion of the hydroxyl ions. The effects of current density, time, and hydrodynamic conditions on coating weight, cell voltage, temperature, and pH of the solution were studied.