We report binary nanoparticle superlattices obtained by self-assembly of two different semiconductor quantum dots. Such a system is a means to include two discretized, quantum-confined, and complimentary semiconductor units in close proximity, for purposes of band gap matching and/or energy transfer. From a range of possible structures predicted, we observe an exclusive preference for the formation of Cuboctahedral AB(13) and AB(5) (isostructural with CaCU5) obtained in the system of 8.1 nm CdTe and 4.4 nm CdSe nanoparticles. For this system, a possible ionic origin for the formation of structures with lower packing densities was ruled out on the basis of electrophoretic mobility measurements. To understand further the principles of superlattice formation, we constructed space-filling curves for binary component hard spheres over the full range of radius ratio. In addition, the pair interaction energies due to core-core and ligand-ligand van der Waals (VDW) forces are estimated. The real structures are believed to form under a combined influence of entropic driving forces (following hard-sphere space filling principles) and the surface (due to ligand-ligand VDW).