Heteroatom doping in carbonaceous materials is an effective way to improve the performance of super capacitors. Herein, the N/B-co-doped ordered mesoporous carbon spheres (N/B-OMC) were developed by a facile ionothermal strategy. The ordered mesoporous phenol/formaldehyde resin (PF) spheres were employed as carbon precursor, which was treated by ionothermal process using 1-butyl 3-methylimidazole tetrafronoroborate ([Bmim]BF4) as medium. The [Bmim]BF4 can be absorbed in the pores of PF spheres, leading to N/B-co-doping for the obtained carbon framework without damage in spherical morphology and ordered mesoporous structure. As a result, the dual-heteroatom doping, high surface area and enlarged mesopore size of N/B-OMC can enhance the electrochemical performance, exhibiting its promising as novel electrode materials. (c) 2020 Elsevier Inc. All rights reserved.