A regular 2D array of crown molecules, which would spontaneously self-assemble into disordered molecular clusters, is obtained by exploiting a guest-host process, based on the chemical affinity between amino and carboxylic groups on a gold surface. First a carboxylic organic template is formed, which then serves as a host for amino-functionalized crown molecules. The amino-carboxylic interaction thereby drives the formation of a monolayer of guest molecules, regularly distributed at the nanometer scale, preventing their aggregation in unordered clusters observed on a bare gold surface. This method, which can be applied to other guest molecules, represents a novel route to overcome the shape-matching requirements of the standard guest-host architectures. Furthermore, it is intrinsically selective, due to the chemical nature of the anchoring process.