Understanding the phase separation mechanism of solid-state binary compounds induced by laser-material interaction is a challenge because of the complexity of the compound materials and short processing times. Here we present xenon chloride excimer laser-induced melt-mediated phase separation and surface reconstruction of single-crystal silicon carbide and study this process by high-resolution transmission electron microscopy and a time-resolved reflectance method. A single-pulse laser irradiation triggers melting of the silicon carbide surface, resulting in a phase separation into a disordered carbon layer with partially graphitic domains (∼2.5 nm) and polycrystalline silicon (∼5 nm). Additional pulse irradiations cause sublimation of only the separated silicon element and subsequent transformation of the disordered carbon layer into multilayer graphene. The results demonstrate viability of synthesizing ultra-thin nanomaterials by the decomposition of a binary system.