One of the primary challenges in electrocatalysis for the hydrogen evolution reaction (HER) lies in the development of highly efficient catalysts suitable in acidic environments. Tungsten carbide-based materials have long been proposed as potential substitutes for Pt due to their “Pt-like” electronic properties in the HER process. However, tungsten carbide still falls short of the performance exhibited by commercial precious-metal catalysts. Herein, PtRuW/WC was prepared by a microwave heating method and acted as a HER electrocatalyst. The microwave method not only enhances the diffraction peaks of the substrate tungsten carbide, but also facilitates the growth of metal ions at specific sites. The PtRuW/WC catalyst demonstrates outstanding performance in acidic HER, characterized by a minimal overpotential of 40.7 mV at 10 mA/cm2 (η10). Furthermore, it exhibits exceptional stability in acidic solutions, showing no substantial degradation during 20 h at 1000 mA/cm2. The catalyst-assembled PEM electrolytic water electrode further proves that PtRuW/WC has excellent electrolytic water performance and makes some efforts for the development of commercial PEM electrolytic water.