Understanding the physical and chemical processes in which local interactions lead to ordered structuresis of particular relevance to the realization of supramolecular architectures on surfaces. While spectacularpatterns have been demonstrated on metal surfaces, there have been fewer studies of the spontaneousorganization of supramolecular networks on semiconductor surfaces, where the formation of covalentbonds between organics and adatoms usually hamper the diffusion of molecules and their subsequentinteractions with each other. However, the saturation of the dangling bonds at a semiconductor surface isknown to make them inert and offers a unique way for the engineering of molecular patterns on thesesurfaces. This review describes the physicochemical properties of the passivated B-Si(111)-(√3x√3) R30°surface, that enable the self-assembly of molecules into a rich variety of extended and regular structureson silicon. Particular attention is given to computational methods based on multi-scale simulations thatallow to rationalize the relative contribution of the dispersion forces involved in the self-assemblednetworks observed with scanning tunneling microscopy. A summary of state of the art studies, where afine tuning of the molecular network topology has been achieved, sheds light on new frontiers for exploitingthe construction of supramolecular structures on semiconductor surfaces