The preparation of noble‐metal‐free electrode materials that enable the effective and economically viable hydrogen evolution reaction (HER) is proposed by using a needle‐less electrospinning method. Three transition metals (Ni, Co, Cu) capable of creation metal phosphides were stably incorporated into the carbon fibrous matrix. The electrode materials were prepared from low‐cost chemical reagents such as polyacrylonitrile, metal chlorides, and phosphoric acid. The embedded metal phosphides fundamentally influence the composition, microstructure, and porosity as evidenced by X‐ray diffraction (XRD), Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) analyses. The possible mechanisms for the formation and localization of nanoparticles were suggested. Linear sweep voltammetry, impedance spectroscopy, time of flight (TOF) calculation, and Tafel slope measurements in an acidic environment revealed that the highest electrocatalytic activity for HER was achieved in the carbon fibers decorated either with the cobalt/cobalt phosphide or copper/copper phosphide nanoparticles under heat treatment in a hydrogen atmosphere.