Porous carbide-derived carbons (CDCs) are synthesized from different carbide (VC, TiC, NbC) as electrode materials for electrochemical capacitors. The process of carbide–carbon transformation is investigated by observations at different carbide/CDC interfaces. It is found that the restructuring process has much influence on formation of microstructure as well as the resultant electrochemical performance. The carbon structure in the produced CDC is well in accordance with that formed at the carbide/CDC interface, indicating that the microstructure in the produced CDC is decided by re-bonding of the residual carbon atoms. It is further found that the internal stress during carbide–carbon transformation has much influence on the CDC microstructure. In addition, the microstructure in CDCs is dependent on the volumetric concentration of carbon atoms in carbide precursor. Lower volumetric concentration of carbon atoms facilitates the formation of CDC with short and curved graphene structure, which owns easily accessible pores and large specific surface area, and thus high electrochemical performance for ultracapacitor. A novel strategy that controlling microstructure of CDC through controlling the volumetric concentration of carbon atoms in carbide precursor is presented. This strategy is very effective to form designed microstructure of CDC for electrochemical applications.