Addressed herein is the preparation and the electrode performance of monodisperse CoFe2O4 nanoparticles (NPs) supported on Vulcan XC-72 for the Lithium-air battery (LAB) and Lithium-ion battery (LIB). Monodisperse CoFe2O4 NPs were synthesized by the thermal decomposition of cobalt(II) acetylacetonate and iron(III) acetylacetonate in oleylamine and oleic acid in the presence of 1,2-tetradecanediol and benzyl ether. As-prepared CoFe2O4 NPs with a particle size of 11 nm were then supported on Vulcan XC-72 (Vulcan-CoFe2O4) at different theoretical loadings (20, 40 and 60 wt % CoFe2O4 NPs) by using the simple liquid phase self assembly method. CoFe2O4 NPs dispersed on Vulcan-CoFe2O4 composites were characterized by transmission electron microscopy (TEM), powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS). The AAS analyses indicated that the Vulcan-CoFe2O4 composites with different loadings were included 3.7, 8.1 and 16.4 wt % CoFe2O4 on the metal basis. The electrode performance of Vulcan-CoFe2O4 composites were evaluated as the anode active material for LIB and cathode active material for LABs by performing the galvanostatic charge–discharge tests. The highest discharge capacity for both LAB (7510 mAh g(Vulcan+CoFe2O4) −1; 13380 mAh gCoFe2O4 −1 @ 0.1C) and LIB (863 mAh g(Vulcan+CoFe2O4) −1; 9330 mAh gCoFe2O4 −1@ 0.1C) was investigated with 16.4 wt % CoFe2O4.