The nucleation and growth of four types of molecular crystals (4,4-diiodobiphenyl, 2-methyl-4-nitroaniline, 3-nitroaniline, and 2-amino-5-nitropyridine) on gold-thiol self-assembled monolayers (SAMs) of 4'-X- and 3'-X-4-mereaptobiphenyl (X = I and NO2) is described herein. In each case, crystals were found to nucleate heterogeneously on the SAM template and adopt specific growth orientations with respect to the underlying monolayer surface. The preferred orientations observed in these and other systems can be rationalized on the basis of coincident epitaxy and complementary (NOI)-I-... interactions across the SAM/crystal interface.