One-pot solvothermal process is adopted to develop, 3D hierarchical Fe3O4 nanoparticles supported 2D reduced graphene oxide sheets (Fe3O4/r-GO) as possible negative electrodes for lithium ion batteries. The synthesis parameters are optimized to prepare agglomeration-free Fe3O4 nanostructures with uniform size and shape on r-GO. The field emission scanning electron microscopic (FESEM) image reveals that the 3D hierarchical Fe3O4 nanostructures are uniformly decorated on r-GO. The physicochemical and functional properties of Fe3O4/r-GO are systematically investigated using various techniques. The fabricated Fe3O4/r-GO electrode delivers an initial discharge capacity of 1221 mAh g(-1) at a current density of 100 mA g(-1) and retains the specific capacity of 1560 mAh g(-1) after 100 cycles. Fe3O4/r-GO significantly enhances cyclic performance, when compared with bare Fe3O4 nanoparticles due to the uniform distribution of Fe3O4 nanoparticles on the graphene sheet with the more number of electrochemically active sites.