A simple, mild, and efficient method for the cyanation of stable arenediazonium salts was developed with polymer-supported cyanide. Arenediazonium hydrogen sulfate (Ar?N2+HSO4-) was obtained by the reaction between a primary aryl amine and sodium nitrite in the presence of concentrated sulfuric acid (H2SO4) at low temperature (05 degrees C). By an ion-exchange reaction between Ar?N2+HSO4- and NaBF4, the stable arenediazonium tetrafluoroborate, Ar?N2+BF4-, was prepared. Ar?N2+BF4- was then converted to aryl nitrile with crosslinked poly(4-vinylpyridine) supported cyanide ion in acetonitrile at room temperature. The spent polymeric reagent was regenerated and reused several times without any loss in its activity. This procedure offered advantages, including a higher isolated yield, shorter reaction time, and simple reaction workup. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012