Abstract The thermal and electron-induced chemistry of CH 3N 2CH 3 on Ag(111) has been studied using temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). CH 3N 2CH 3 adsorption on Ag(111) is completely reversible, with desorption peaks at 180 and 130 K for monolayer and multilayer, respectively. Electron irradiation on 1 ML of CH 3N 2CH 3 results in almost quantitative electron stimulated desorption (ESD) of N 2. ESD of CH 3 and CH 4, as well as traces of C 2H 6 and C 2H 2, is also observed. The retained fragments desorb in TPD mainly as H 2 and CH 4. At 54.7 ± 0.3 eV, the electron-induced decomposition (EID) cross section is about 7 × 10 −17 cm 2. The EID cross section increases with electron energy and has a threshold of about 10 eV. The EID is attributed to ionization of chemisorbed azomethane.