Crosslinked poly (4-vinylpyridine)-supported azide ion was used as an effective azidating agent for deazodination of stable arenediazonium salts under solvent-free conditions in high yields. The diazotization of aromatic amines was prepared by grinding the combination of an aromatic amine, sodium nitrite (NaNO2), p-toluene sulfonic acid (p-TsOH), and 0.2 mL H2O in a mortar. Grinding was continued for deazodinationazidation of the obtained relatively stable diazonium salts, with addition of crosslinked poly (4-vinylpyridine) supported azide ion to obtain the corresponding aryl azides. The spent polymeric reagents can usually be removed and regenerated. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012