The BiF 3 /AlPO 4 composite has been synthesized using the mixture of as-prepared BiF 3 and amorphous AlPO 4 powder as the starting materials by solid state method. The structure and morphology of AlPO 4 and BiF 3 /AlPO 4 composite have been characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). The electrochemical performance of BiF 3 /AlPO 4 composite has been studied by galvanostatic charge/discharge, cyclic voltammetry (CV) measurements. The results show that the as-prepared AlPO 4 is amorphous, and the addition of amorphous AlPO 4 does not change the bulk structure of BiF 3 , but AlPO 4 is only coated on the surface of BiF 3 forming the BiF 3 /AlPO 4 composite. Electrochemical measurements in the voltage range of 1.5–4.5 V reveal that the addition of amorphous AlPO 4 can effectively reduce the effect of solid electrolyte interface (SEI) and markedly improve the electrochemical performance of BiF 3 in the EC:DMC electrolyte. And the BiF 3 /AlPO 4 composite delivers an initial discharge capacity of 271.5 mAh g −1 and a reversible capacity of 209.1 mAh g −1 at a current density of 30 mA g −1 . Furthermore, the BiF 3 /AlPO 4 composite also exhibits enhanced rate capability and acceptable cycle performance.