Mesoporous LiFePO4/C composites containing 80 wt% of highly dispersed LiFePO4 nanoparticles (4–6 nm) were fabricated using bimodal mesoporous carbon (BMC) as continuous conductive networks. The unique pore structure of BMC not only promises good particle connectivity for LiFePO4, but also acts as a rigid nano-confinement support that controls the particle size. Furthermore, the capacities were investigated respectively based on the weight of LiFePO4 and the whole composite. When calculated based on the weight of the whole composite, it is 120 mAh·g−1 at 0.1 C of the high loading electrode and 42 mAh·g−1 at 10 C of the low loading electrode. The electrochemical performance shows that high LiFePO4 loading benefits large tap density and contributes to the energy storage at low rates, while the electrode with low content of LiFePO4 displays superior high rate performance, which can mainly be due to the small particle size, good dispersion and high utilization of the active material, thus leading to a fast ion and electron diffusion.