By using large mesoporous carbon (LMC) as a novel host matrix, LMC–FePO4 nanohybrid has been synthesized through a facile homogeneous precipitation process and subsequent annealing approach. When evaluated as a cathode for lithium-ion batteries (LIBs), the LMC–FePO4 nanohybrid exhibits higher specific capacities, improved rate capability, and better cycling performance by virtue of its unique structural characteristics.