The I–V behavior of self-assembled monolayers of a 1,3-alternate bis(dipyridyl)calix[4]arene derivative and its Cu2+ complex have been studied by conducting-atomic force microscopy; theoretical calculations have been carried out to simulate I–V curves. The experimental data show that the two systems have different conductive properties, the Cu2+ complex monolayer having a lower resistance. Theoretical calculations demonstrate that the difference between the two simulated systems results from the different position of their Fermi level. Such a different response to charge transfer may be of interest for the fabrication of molecular electronics devices based on calixarenes.