Two-dimensional (2D) materials have attracted significant research interests for energy-storage applications owing to their unique structural and electronic properties. The modification of 2D materials with ordered mesoporous carbon (OMC) offers great opportunities for increasing the ion-accessible surface area and improving the ion diffusion. Herein, we report an unprecedented type of heterostructured MXene (Ti3C2Tx)/nitrogen-doped OMC (NOMC) hybrid, which is prepared via the self-assembly of melamine resol-P123 micelles with exfoliated Ti3C2Tx nanosheets. The NOMC exhibits well-ordered mesopores which are aligned with Ti3C2Tx nanosheet surface. This novel structure not only prevents the stacking of MXene nanosheets, but also provides a fast ion-diffusion path. When used as an electrode material for supercapacitors, the Ti3C2Tx-NOMC hybrid exhibits a high gravimetric capacitance of 329 F g−1 and a volumetric capacitance of 823 F cm−3. Furthermore, the Ti3C2Tx-NOMC composite also displays excellent rate capability and good cycling stability, thus highlighting the benefit of hybridizing MXene with ordered mesoporous carbon for for enhancing the energy storage performance.