Herein, the intermolecular hydroamination of alkenes and alkynes with anilines catalyzed by HOTf under mild conditions has been developed. This reaction provides one of the simplest alkene and alkyne addition methods and is an alternative to metal-catalyzed reactions. At the same time, the intramolecular hydroamination of alkynes with anilines proceeds smoothly to obtain quinolines. We found that this strategy is efficient in building complex structures from simple starting materials in an environmentally benign fashion.