We present a mechanism to form self-assembled functional gradient superlattice structures by subjecting binary nanoparticles in an electric field. The interaction among different dipoles leads to the controllable formation of diverse structures, including particle columns with gradient material properties from inside to outside and various hierarchical layered or three-dimensional particle chain networks. We elucidate how permittivity, volume fraction, particle size, and the frequency of the electric field can be utilized to control the morphology of the induced structures, which would enable designed nanofabrication.