Self-organization of 3,5-dihydroxybenzylalcohol (DHBA) based dendrimers of generations 0-3 (G0-G3) on bare and functionalized single crystal silicon (Si/SiO2) surfaces has been examined. The underlying monolayer plays a significant role in the supramolecular assembly leading to ordered structures of DHBA (G0) and generation 1-3 (G1-G3) dendrimers at interfaces. Ordered hyperbranched structures are formed on surfaces containing self-assembled monolayers with complimentary features to the assembling molecules, whereas no such organized assemblies are observed on unfunctionalized surfaces.