Abstract The Copper Catalyzed Azide-Alkyne Cycloaddition (CuAAC) is a paradigm of ¡§click¡¨ chemistry which has been applied in different fields. To understand the interaction between organic azides and a copper surface, we use benzyl azide (Bn¡ÐN£\¡ÐN£]¡ÝN£^) as an adsorbate on Cu(111) under ultrahigh vacuum conditions. The thermal reaction process was explored by a combination of temperature-programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and X-ray photoemission spectroscopy (XPS) techniques. The TPD profiles show a multilayer desorption peak at 190K, two peaks for N2 , and H2 from 270K to 390K. At 345K, peak of desorption product (m/z=103) represents phenyl cyanide (PhCN) or phenyl isocyanide (PhNC). RAIR and XP spectra demonstrate that at 190K benzyl azide on Cu(111) readily adopt the imine intermediate formalism involving N£\¡ÐN£] scission and phenyl group shift from carbon to nitrogen. The mechanism is analogous to the organic reaction of Schmidt rearrangement. To heat the surface to 250K, the CH2 group of the imine intermediate undergoes C¡ÐH bond scission to produce a surface isocyanide intermediate, (M=C=N¡ÐPh). Therefore the final desorption product is phenyl isocyanide at ~350K. Intriguingly, the thermal chemistry of benzyl azide involves both imine and isocyanide intermediacy, despite the fact that azido species usually generate nitrene or imido complexes under thermal conditions.