In the present work, results of electrochemical evaluation, as well as morphological and structural characterization of Ni_xW_1−x materials with x=0.77, 0.64, 0.4, 0.19 and 0.07 processed by means of high energy ball milling from high purity powders are presented. Also, the electrocatalytic performance on the hydrogen evolution reaction (HER) of the Ni_xW_1−x materials evaluated by linear polarization and cyclic voltammetry techniques in alkaline media at room temperature is discussed. The structural and morphological characterization of the as-prepared materials was carried out using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Results indicated a small-particle clusters and solid solution formation. According to the kinetics parameters the best electrocatalytic activity was observed at Ni₆₄W₃₆.