The chemical activation of nitrous oxide (N2O) typically results in O-atom transfer and the extrusion of N-2 gas. In contrast, reactions of N-trimethylsilyl (TMS)-substituted amides with N2O give inorganic or organic azides, with concomitant formation of silanols or siloxanes. N-TMS-substituted amides are also able to induce N-O bond cleavage in N2O-derived dialkylaminodiazotates, generating tetrazene salts. These results indicate the potential of silyl groups in devising transformations, in which N2O acts as an N-atom donor.