Nowadays, continuous scientific endeavors are being directed toward low-cost, mild, scalable and reliable synthesis of graphene-based materials, in order to advance various graphene-related applications. So far, specific surface areas of current bulk graphene powders or graphene-like nanosheets are much lower than the theoretical value (2630 m2 g−1) of individual graphene, remaining a challenge for carbon chemists. Herein, mesoporous graphene-like carbon sheets with high specific surface area (up to 2607 m2 g−1) and high pore volume (up to 3.12 cm3 g−1) were synthesized by using polyimide chemistry in the molten salt “solvent.” In this process, abundant pyromellitic dianhydride and aromatic diamine undergo polycondensation together with further carbonization in molten KCl–ZnCl2, in which in situ formed linear aromatic polyimide with a sp2 hybridized carbon skeleton could be directly coupled and rearranged into a two-dimensional graphene-like nanosheet around the “salt scaffold”. Carbon nanosheets with well-defined mesopores (3.5 nm) could be easily obtained by washing salt melts in water, while the salts could be recovered and reused for the subsequent reaction. The nitrogen atoms in amine also afforded the resulting carbon with uniform foreign atoms (nitrogen content = 6%). Moreover, holey carbon sheets with well-dispersed and through-plane nanoholes (diameter: 5–10 nm) could be constructed by using different monomers. Being a potential electrode material in supercapacitors, the as-made carbon nanosheet possessed a significant specific capacitance (131.4–275.5 F g−1) even at a scan rate of 2000 mV s−1. Additionally, powerful nanohybrids of carbon sheet–Co3O4 were also prepared with good performance in the aerobic oxidation of alcohols and amines to aldehydes and imines, respectively.