Metal sulphide electrocatalyst is considered as one of the most promising low-cost candidates for oxygen evolution reaction (OER). In this work, we report a novel free-standing Cu2S branch array via a facile TiO2-induced electrodeposition-sulfurization method. Interestingly, cross-linked Cu2S nanoflake branch is strongly anchored on the TiO2 backbone forming high-quality Cu2S/TiO2/Cu2S core-branch arrays. The branch formation mechanism is also proposed. As compared to the pure Cu2S nanowire arrays, the as-prepared Cu2S/TiO2/Cu2S core-branch arrays show much better alkaline OER performance with lower overpotential (284 mV at 10 mA cm−2) and smaller Tafel slope (72 dec−1) as well as enhanced long-term durability mainly due to larger exposed area and more active electrocatalytic sites. Our work provides a new way for construction of advanced metal sulphide electrocatalysts for electrochemical energy conversion.