Recently, Co(OH)2 has gained much attention as a promising electrocatalyst. Herein, we synthesized Co(OH)2-decorated TiO2 film for electrocatalytic water splitting by a facile and low-cost electrochemistry method, which possessed enhanced performance for oxygen evolution reaction. The results of X-ray diffractometry, transmission electron microscope, scanning electron microscope and X-ray photoelectron spectroscopy verify the successful decoration of Co(OH)2 electrocatalysts onto the surface of TiO2. Moreover, photoelectrocatalytic measurements illustrate that the Co(OH)2-decorated TiO2 shows higher current density than pure TiO2 sample. The results obtained in this work give deep insights into the development of photoelectrochemical water splitting.