Abstract1‐(Trimethylsilylmethyl)benzotriazole is readily prepared from benzotriazole and chloromethyltrimethylsilane. It undergoes fluoride‐catalyzed desilylation with carbonyl compounds and forms an anion that can be alkylated and acylated readily and undergoes Peterson olefination. 1‐(Cyclohexylidenemethyl)benzotriazole is lithiated exclusively at the α carbon atom, and the anion can be cleanly alkylated.1‐(α‐Acylalkyl)benzotriazoles are reduced to ketones with zinc and acid. The stability of 1‐alkenylbenzotriazoles to hydrolysis has