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Developing a catalyst for improving the efficiency of water electrolysis is one of the current research hotspots. Herein, we design and fabricate a nested-like Ce-doped CoP nanowires on carbon cloth. The Ce-CoP NWs/CC catalyst with optimized amounts of Ce-doping (6%) exhibits excellent hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performance as well as preeminent overall water splitting (OWS) in alkaline media. As a high-performance and durable electrocatalyst, Ce-CoP NWs/CC presents low overpotentials with 80 and 290 mV at 10 mA cm -2 for HER and OER, outperforming many reported non-noble metal catalysts. Moreover, the assembled water-splitting device exhibits a voltage of only was also 1.506 V at 10 mA cm -2 . This work provides an efficient and inexpensive catalyst for overall water splitting.