Mesoporous LiFePO4/C microsphere was successfully prepared by spray drying assisted template method (SDATM) with citric acid as a template. This material has an average pore size of 50nm and gives large specific surface area (32.2m2 g−1) with evenly distributed carbon (4.3wt.%). It is also easy to bring into contact with electrolyte, facilitate the electric and lithium ion diffusion. It presents large reversible capacity of 158.8mAhg−1 at C/10, even high rate capacity of 59.7mAhg−1 at 20C, and excellent capacity retention rate closed to 95.5% after various current densities.