We have explored in detail the potential energy surfaces of the Si5Lin5-6 (n = 5-7) systems. We found that it is feasible to design three-dimensional star-like silicon structures using the appropriate ligands. The global minimum structure for Si5Li7+ has a perfect seven-peak star-like structure. The title compounds comprise, essentially, the Si-5(6-) ring interacting with lithium cations. The ionic character of the Si-Li interactions induces the formation of a bridged structure. Concomitantly, our calculations show that the reduction of the Pauli repulsion and the maximization of the orbital contribution are also significant for the star-like structure formation. Additionally, the MO analysis of the systems suggests that the role of the lithium atoms is to provide the precise number of electrons to the central Si-5 unit. This is confirmed by the magnetic properties, which show that electron delocalization enhances the stability of the star-like structures proposed here.