In this work, the composites of nitrogen-doped graphene framework and Co3O4 nanoparticles with adjustable morphologies (NG/Co3O4) were fabricated via a surfactant-assisted hydrothermal route for first time. Three different surfactants including triblock copolymer F127, cetyltrimethyl ammonium bromide and sodium dodecyl sulfate are involved in the hybrid-assembly of graphene oxide, o-phthalonitrile and cobalt acetate in water/ethanol. Among the obtained samples, the one using F127 (NG/Co3O4-F127) manifests the most homogeneous distribution of Co3O4 NPs with the size of∼15nm in the macropore-walls formed by NG. As the anode material in lithium ion battery (LIB), NG/Co3O4-F127 exhibits excellent electrochemical performance, which is superior to the other composites and most of the previously reported Co3O4 based anode materials in LIBs.