We have developed a low-temperature atomic layer deposition (ALD) process for depositing crystalline and phase pure spinel cobalt oxide (Co₃O₄) films at 120 °C using [Co(^tBu2DAD)₂] and ozone as coreagent. X-ray diffraction, UV-vis spectroscopy, atomic force microscopy, field emission scanning electron microscopy, X-ray photoelectron spectroscopy, and time-of-flight elastic recoil detection analysis were performed to characterize the structure and properties of the films. The as-deposited Co₃O₄ films are crystalline with a low amount of impurities (<2% C and <5% H) despite low deposition temperatures. Deposition of Co₃O₄ onto thin TiO₂ photoanodes (100 nm) for water oxidation resulted in 30% improvement of photocurrent (after 10 ALD cycles yielding small Co₃O₄ particles) as compared to pristine TiO₂ films), and exhibited no detrimental effects on photocurrent response up to 300 deposition cycles (approximately 35 nm thick films), demonstrating the applicability of the developed ALD process for deposition of effective catalyst particles and layers in photoelectrochemical water-splitting devices.