Spherical LiFePO4 was synthesized by one-step solvothermal method, and then the spherical LiFePO4/C with porous surface was formed by soaking carbon in saturated glucose solution. The purity, composition, crystal morphology and the porous structure of the cathode materials were characterized by XRD, SEM, HRTEM, FTIR, BET respectively. The experimental results showed that the porous surface structure made the porous spherical LiFePO4/C have a larger specific surface area and more active sites, which greatly reduced the migration distance of lithium ions in the process of charge and discharge and reduced the resistance of lithium ions diffusion and disintegration in the material. Under the premise of maintaining a high tap density (1.36 g·cm-3), the utilization rate of the material was further improved and the large rate charge-discharge performance of the material was larger. The electrochemical testing results showed that the spherical structured LiFePO4/C with porous surface had better electrochemical performance.