We demonstrate by computer experiments that the spontaneous to of two-dimensional regularly patterned molecular networks containing voids may be an entirely entropy-driven process. On the basis of a simple model of core (soft) shell half-disk-shaped particles, we show that, even without the mediation orally attractive interparticle forces, such particles self-organize to stable and macroscopically ordered patterns with regularly distributed voids. The morphology of these supramolecular porous motifs depends critically on the size of the core relative to the coronal halo. The reverse engineering analysis of these precise two-dimensional supramolecular porous templates suggests molecular-shape complementarity and polyphilicity as key design parameters for the bottom-up engineering of such functional substrates.