tert-Butyl nitrite (TBN) is an important metal-free reagent that is widely applied in various organic transformations. Besides its traditional applications in nitrosation and diazotization, its ability to activate molecular oxygen to enable the initiation of radical reactions, including nitration, oximation, oxidation, and so on, has attracted extensively attention in the past decade. This review highlights recent advances in this field to promote further exploration of this versatile compound. 1 Introduction 2 Reactions Involving TBN 2.1 Nitrosation 2.2 Oximation 2.3 Diazotization 2.4 Nitration 2.5 Oxidation 2.6 Other Reactions 3 Conclusion and Perspective