Bifunctional electrocatalysts that exhibit excellent catalytic activity for both hydrogen (HER) and oxygen evolution reactions (OER) are ideal for alkaline overall water splitting. The unique structure and diverse composition of cobalt phosphide catalysts are highly favorable for enhancing catalytic reaction kinetics. However, cobalt phosphide electrocatalysts typically exhibit insufficient OER activity. To overcome this text, we synthesized a Ru and V co-doped CoP-coupled highly conductive MXene catalyst with nano-arrays by in-situ growth on the surface of carbon cloth. The HER and OER overpotentials of the catalyst at 10 mA cm−2 current density were 30 and 206 mV, respectively. Furthermore, a series of physicochemical characterizations and first-principles calculations demonstrated that the increased HER and OER activities resulted from the synergistic effect established by the double doping and heterostructure. This effect produced an effective modulation of the d-band center of the catalysts, promoting adsorption effects on the intermediates. In conclusion, this work presents a novel approach to improving the electrocatalytic activity of phosphides and provides a faster and more environmentally friendly method for separating hydrogen from water.