The hydrogen evolution reaction (HER) plays a vital role for the production of pure hydrogen with zero carbon release. Developing high efficiency non-noble metal electrocatalysts could reduce its cost. Here, vanadium doped cobalt phosphide grown on carbon cloth (CC) was synthesized by the low temperature electrodeposition-phosphorization method. The influence of V dopants on the structural, morphological, and electrocatalytic performance of Vx-Co1-x-P composites was also investigated in-depth. Impressively, the optimized amorphous V0.1-Co0.9-P nano-electrocatalyst exhibits outstanding catalytic activity with a low overpotential of 50 mV at a current density of 10 mA cm-2 and a small Tafel value of 48.5 mV dec-1 in alkaline media. The results showed that V dopants in the composite change its crystal structure from the crystalline phase to the amorphous phase, resulting in the introduction of V-O sites, which regulate the electron density of the active sites and the exposure of surface active sites and thus promote the electrocatalytic HER process. This work provides a novel idea for the fabrication of high-efficiency metal phosphide based electrocatalysts.