The synthesis and design of non-precious and efficient electrocatalysts by an eco-friendly technique are required for renewable and clean energy. This work reports a successful synthesis of nickel-cobalt phosphide (Ni-Co-P) anchored on carbon fiber cloth (CFC) for advanced electrocatalytic applications. Detail structural and morphological analyses reveal that the interfacial growth of Ni-Co-P on CFC possesses a unique hexagonal sheet exteriorly decorated with nanoneedles around the edges depicting a cactus-like morphology. This Ni-Co-P/CFC exhibits unprecedented electrocatalytic activity for hydrogen evolution reaction (HER) with a current density of 10 and 200 mA cm⁻² acquires at the overpotential of 43 and 149 mV versus reversible hydrogen electrode (RHE), respectively. Based on cyclic-voltammetry (CV) and Tafel plot results, it is deduced that this high activity is mainly credited to the large surface area and a large number of active sites from the hexagonal multilayer-sheet decorated with nanoneedles profile. Moreover, no significant deactivation is observed even after running for 12 h or at least 2000 CV cycles, suggesting excellent stability, making it a promising electrocatalyst. It is expected that our work could provide a new strategy to design non-precious and efficient electrocatalysts for practical applications with highly-active and better-durability for HER.