A powerful mode of reactivity to re-emerge in recent years to rapidly assemble molecular complexity from simple precursors is radical chemistry involving the intermediacy of a nitrogen-centred radical species.1 In this presentation, we will disclose our contributions to this important facet of chemical synthesis. We will highlight recent studies for the site-selective C(sp3)–H bond functionalisation such as the realisation of a copper(I)-catalysed method for chlorination at the γ-position of ketones and (E)-1,3-enones, and benzylic position of alkylbenzenes.2 A photoinitiated method mediated by dichloramine-T for the α-functionalisation and α,β-difunctionalisation of a variety of saturated N- and O-heterocycles will also be unveiled.