Efficient and abundant electrocatalysts are very important for practical hydrogen evolution from the electrocatalysis of water on large-scale. Therefore, it is necessary to study the intrinsic electrocatalytic hydrogen evolution properties of materials. Here, for the first time, we used the 2D Na_xWO_y as precursor to prepare various W-based compounds (WC_1–X, WS₂, WP, W₂N₃, and WN) and compared their electrocatalytic activity of the hydrogen evolution reaction (HER). WC_1–X has the best HER performances with a low overpotential (216 mV in base and 247 mV in acid solutions at 10 mA cm^–2) and good long-term durability. Furthermore, WC_1–X shows low interfacial transfer resistance and large electrochemically active surface areas, suggesting its high conductivity and rich active sites, and thus resulting in the superior electrocatalytic HER activity. Meanwhile, the first-principles calculations reveal that WC_1–X presents the highest HER activity among these compounds because the ΔG_H is very near to zero. We hope that our work will offer guidance for the design of electrocatalysts with high activity for practical applications.