Nanoarchitecturing of carbon with assembled building blocks in diverse scales with superior physical properties and tunable chemical characters is of great importance for energy storage. Therefore, exploring boron-modified ordered mesoporous carbons (OMCs) with tailorable microstructure and controllable incorporation become scientifically necessary. In this contribution, the boron-rich ordered mesoporous carbons were formed via a solvent evaporation-induced self-assembly strategy with controllable boron incorporation, tailorable microstructure, and extraordinary electrochemical capacitance. The incorporated boron content can be verified from 0 to 1.64 wt%, and the obtained B-OMCs exhibited widened potential window and enhanced specific capacitance. A maximum value of B incorporation (1.01–1.35 wt%) was detected in improving the specific capacitance (0.38–0.39 Fm⁻²). This is attributed to the specific oxygen chemisorption and the strengthened surface polarization accompanied with B modification. These results demonstrate the material chemistry, widen the potential applications, and in consequence allow mechanistic insight into the roles boron played for OMC textures and electrochemical activities.