Ordered multimodal porous carbon (OMPC) with a hierarchical nanostructure was prepared and explored as an anode for Li ion batteries. OMPC possesses unique structural characteristics, such as large surface area and mesopore volume, particularly the multimodal porosity composed of a well-developed 3D interconnected ordered macropore framework with open mesopores embedded in the macropore walls, which facilitate fast mass transport and charge transfer. Compared with ordered mesoporous carbon CMK-3, the OMPC not only demonstrates higher Li storage capacity, but also better cycling performance and rate capability. The enhancement in anode performance especially in cycling performance and rate capability is mainly attributable to the superb structural characteristics of the OMPC, particularly the open larger mesopores located in the ordered macropores, which act as efficient Li storage and buffer reservoirs to reduce volume change during the charge–discharge cycling especially at high rates.