We describe the engineering of a supramolecular self-assembly on a siliconbased surface. This assembly was achieved by using a Si(111)- B √3 x √3 R30° reconstruction surface and 1,3,5-tri(4’-bromophenyl) benzene (TBB) as molecular building block. The growth of a supramolecular network is controlled by tuning molecule–molecule interactions and molecule–silicon substrate interactions. This robust open honeycomb network controls the growth and serves as a template of a noncompact hexagonal fullerene array from 100 to 370 K.