The functionalization of metal surfaces with small organic molecules allows for obtaining hybrid interfaces with specific morphologic and electronic properties. In particular, the formation of 2D architectures, ordered at the nanoscale, provides prototypes of smart electrodes, able to act as templates for the assembly of organic films. The chemical affinity between functional groups can be exploited both to drive the growth of the complex architectures and to improve their electronic transport properties. In this view, we have explored the morphology and electronic properties of hetero- and homo-organic 2D templates, based on amino-carboxylic and boronic molecules respectively. By applying a multi-technique approach, combining STM microscopy, X-ray spectroscopies and DFT calculations, we thoroughly characterized the systems. I will in particular present examples of the templating properties of the architectures we obtained, based on a chemical guest-host approach. The amino-carboxylic affinity is shown to drive the ordered assembly of amino-terminated molecules on a carboxylic template. Moreover, I will discuss the electron transport properties of the functionalized 2D interfaces, as probed by means of resonant photoemission spectroscopy and of the core-hole clock method.