A novel phenol–formaldehyde carbon with ordered/disordered bimodal mesoporous structure is synthesized by the facile evaporation induced self-assembly strategy under a basic aqueous condition with SiO2 particles as template. The prepared bimodal mesoporous carbons (BMCs) are composed of ordered mesoporous and disordered mesoporous with diameter of about 3.5 nm and 7.0 nm, respectively. They can be employed as supercapacitor electrodes in H2SO4 aqueous electrolyte after the simple acid-treatment. BMC exhibits an exceptional specific capacitance of 344 F g−1 at the current density of 0.1 A g−1, although it has a relatively low surface area of 722 m2 g−1. And the BMC electrode displays an excellent cycling stability over 10,000 cycles.