Ce-doped FeVO4 nanocomposites were successfully synthesized using reverse micro-emulsion route. Thermal and microstructural characteristics were comprehensively investigated by simultaneous thermal analysis, X-ray diffraction (XRD), scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy (FT-IR) and laser particle size analyzer. Moreover, as the anode material of lithium-ion batteries, the electrochemical properties were studied by galvanostatic charge and discharge tests and electrochemical impedance spectroscopy. The thermal analysis illustrated that the triclinic crystal structure of FeVO4 nanoparticles is formed at about 520 °C, which is confirmed by XRD and FT-IR results. Furthermore, the microstructural analyses revealed more regular particles and high specific surface area for wet-chemical derived FeVO4:Ce, which decreases the diffusion pathway of the lithium ions during the insertion/extraction process. The electrochemical measurements indicated that the electrode cycling performance and rate retention ability of Ce-doped FeVO4 are better than those of pure FeVO4 due to the expansion of the crystal lattice, which provided more lattice space for lithium intercalation and de-intercalation. Consequently, the as-prepared Ce-doped FeVO4 with relatively high specific and reversible capacity, thermal stability and satisfactory cycling performance is a promising candidate for use as a lithium batteries anode material.