The unique heterocyclic skeletons of N-heterocyclic phosphines (NHPs) endow them with excellent hydridic reactivity, which has enabled NHPs to be applied in a great array of catalytic hydrogenations of unsaturated substrates in the past few decades. Recently, applications of NHPs in radical reductions, especially in a catalytic fashion, have emerged as a promising forefront area. This new reaction pattern, distinctive from but complementary to the well-established hydride pathway, can greatly expand the reaction scope to σ-bond scission. Herein, we briefly summarized some representative examples of synthetic applications of NHPs in both hydridic and radical reductions with an emphasis on their radical reactivity, including the structural and property studies of NHP radicals and their precursors as well as their applications in radical processes.