Single crystal sapphire and diamond surfaces are used as planar, atomically flat insulating surfaces, for the deposition of the diacetylene compound 10,12-nonacosadiynoic acid. The surface assembly is compared with results on hexagonal boron nitride (h-BN), highly oriented pyrolytic graphite (HOPG) and MoS2 surfaces. A perfectly flat-lying monolayer of 10,12-nonacosadiynoic acid self-assembles on h-BN like on HOPG and MoS2. On sapphire and oxidized diamond surfaces, we observed assemblies of standing-up molecular layers. Surface assembly is driven by surface electrostatic dipoles. Surface polarity is partially controlled using a hydrogenated diamond surface or totally screened by the deposition of a graphene layer on the sapphire surface. This results in a perfectly flat and organized SAM on graphene, which is ready for on-surface polymerization of long and isolated molecular wires under ambient conditions.