While the mechanistic details of the dimerization of the self-complementary 2-ureido-4(1H)-pyrimidinone (UPy) motif are well studied in solution, no such investigation is available on a surface. Here we report an extensive study of hydrogen binding kinetics for quadruply H-bonded UPy arrays on aluminum surfaces and explore the ON/OFF capability of such arrays under externally controllable conditions. Also, we investigate the dynamic nature of this system whereby the interfacially H-bonded UPy is displaced by another UPy derivative in solution, and reveal the kinetics of the exchange process.