Mesoporous bowl-like LiFePO4/C composites were synthesized by a wet milling-spray drying-carbothermal reduction (WSC) using starch as the organic carbon source and reductive agent. The samples were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) analysis, cyclic voltammograms (CV), electrochemical impedance spectra (EIS) and galvanostatic charge–discharge testing. Most of the mesoporous bowl-like LiFePO4/C composites with particle size in the range 5–10μm, coated with evenly distributed carbon, were assembled by nanoparticles (<100nm), and had a mesoporous structure with the pore size of 13.30nm and a speciﬁc surface area of 29.40m2 g−1. These delivered a discharge capability of 123mAhg−1 at 10 C, with no capacity loss after 100 cycles. The enhanced electrochemical performance was mainly ascribed to the improved ionic/electronic conductivity and structural stability arising from the interconnected mesoporous pores, carbon-coated nanoparticles and micro-sized structure.