Recent progress on catalytic nitrene transfer reactions with hydroxylamine derivatives as prevalent precursors is summarized in this highlight. The salient features of these N-O derived nitrene transfer reagents are that they are readily available, bench-stable, and can be facilely activated by a range of transition metal-catalysts under mild conditions. The application of these reagents in transition metal-catalysis has led to many new amidation or amination reactions, such as C-H insertions and aziridination of olefins. These reagents have also been applied in difunctionalisation of unsaturated bonds, dearomative amination of indoles, and formation of N-X bonds. Moreover, the recent achievements in photocatalysis and enzyme catalysis further emphasize the importance of these appealing reagents. This highlight provides an overview of these reactions reported in recent years. Challenges and potential opportunities for future developments are also discussed.