The Ni/active carbon (AC) electro-catalyst was prepared by chemical reduction method using coconut carbon as the support. Morphologies and structures of Ni/AC were measured and characterized by X-ray diffraction and scanning electron microscopy. The activity of the Ni/AC membrane electrodes were studied in the neutral electrolyte using Tafel polarization curves and electrochemical impedance spectroscopy (EIS). The results showed that the average size of nickel particles on the active carbon were in nano-size range. The exchange current density of hydrogen evolution reaction (HER) of Ni/AC electro-catalysts was seventy-five times more than pure nickel, so Ni/AC electro-catalysts had better electro-catalytic activity. In 1 mol·L-1 NaCl electrolyte, the Tafelian behavior′s hydrogen evolution reaction (HER) of Ni/AC electro-catalyst at high over-potential existed in two Tefal regions. These two regions were named as "regionⅠ:0.318~0.456 V" and "regionⅡ: 0.120~0.288 V". The rate step of regionⅠ was electron transference step. The rate step of region Ⅱ was concentration polarization.