Electroactive lithium vanadyl phosphate, β-LiVOPO4, was synthesized via a sol–gel route, and β-LiVOPO4/RuO2 composite was subsequently prepared by heating RuCl3 in the network of β-LiVOPO4 particles. X-ray diffraction patterns showed that β-LiVOPO4 has an orthorhombic structure with space group of Pnma. Energy dispersive X-ray spectroscopy dot mappings revealed that ruthenium was homogeneously distributed among β-LiVOPO4 particles. Compared with pristine β-LiVOPO4, β-LiVOPO4/RuO2 composite presented better electrochemical Li ion intercalation performances due to the enhanced electrical conductivity and Li ion diffusion. β-LiVOPO4 may be prospective for the application to high-voltage Li ion batteries if the electrical conductivity is improved through a practical way.