Herein, we developed a fluoride‐mediated nucleophilic aromatic amination of chloro‐1H‐1,2,3‐triazolium salts. Various functional groups were tolerated in this reaction, which enabled the synthesis of functionalized amino‐1H‐1,2,3‐triazolium salts. In addition, we investigated the catalytic properties of triazolium‐based N‐heterocyclic imines (NHIs) for cyanosilylation of ketones. The substituent was found to play a crucial role for inducing high catalytic activity.