Tungsten carbides are important materials used in ceramic cements, machining tools, catalysts, sensors, and for hydrogen generation. Bulk W–C structures are highly complex; fundamental fully carburized WC and semi-carburized W2C are accompanied by structural transitions depending on the composition and temperature. The relationship between the structures, compositions, and temperatures is summarized in the W–C phase diagram. However, the high-temperature, stable, and single-crystalline nanoparticles related to the WC1-x and W2C phases formed via energetic reactions accompanied by rapid cooling rates are not easy to determine considering the bulk phase diagram, and lead to fundamental questions regarding the origin of the nanophases. In this study, we propose a draft for the W–C nanophase diagram composed of the surface and gas-phase WC, WC1-x, and W2C nanophases according to the composition and temperature. The model undergoes the process of a vapor–nanoliquid–nanophase starting from the gas-phase nucleation induced by an extremely high-temperature electrical explosion. In addition, the high-temperature reactivity and quenched nanophase, including its unique nanostructure, are related to the post-melt rheology, physical morphology, and steric hindrance of the solid matrix during an electrical explosion.