Most recently, Vanadium oxide nanoparticles/reduced Graphene oxide (VO-NPs/rGO) nanocomposite have attracted extensive attention due to their potential applications in energy-related areas. Hence, understanding the interactions on behalf the effect of graphene layers on the modification of VO-NPs properties as well as their growth mechanism are of great importance. In this work, our results are revealing that VO-NPs were efficiently grown and coated on the graphene surface and are clearly showing the strong effect of rGO layers on the growth of VO-NPs which leads to a modification in the form, the shape and also the phase. These interactions which were studied based on structural and morphological investigations will play an important role on the modification of these nanocomposites properties which is suitable for a wide range of potential applications and particularly as electrode in Li-ion batteries.