In this paper, W-containing SiC-based ceramic nanocomposites were successfully prepared by a polymer-derived ceramic approach using allylhydridopolycarbosilane (AHPCS) as a SiC source, WCl₆ as a tungsten source, polystyrene (PS) as a pore forming agent as well as divinyl benzene (DVB) as a carbon rich source. High-temperature phase behavior of the W-containing SiC-based ceramics after heat treatment was studied, showing that excessive DVB content in the feed will inhibit the crystallinity of W-containing nanoparticles in the final ceramic nanocomposites. The high specific surface area (SSA) of 169.4-276.9 m²/g can be maintained even at high temperature in the range of 1400-1500 ℃, due to the carbothermal reaction which usually occurs between 1300 and 1400 ℃. All prepared W-containing SiC-based nanocomposites reveal electrocatalytic activity for the hydrogen evolution reaction (HER). In detail, compared with reversible hydrogen electrode (RHE), the ceramic sample PWA-2-1300 after heat treatment at 1300 ℃ has the smallest overpotential of 286 mV when the current density is 10 mA·cm^-2 in acid medium, indicating the promising perspective in the water splitting field.