Abstract Chiral amines are key substructures of biologically active natural products and drug candidates. The advent of photoredox catalysis has changed the way synthetic chemists think about building these substructures, opening new pathways that were previously unavailable. New developments in this area are reviewed, with an emphasis on C–C bond constructions involving radical intermediates generated through photoredox processes. 1 Introduction 2 Radical–Radical Coupling of α-Amino Radicals 2.1 Radical–Radical Coupling Involving Amine Oxidation 2.2 Radical–Radical Coupling Involving Imine Reduction 2.3 Couplings Involving both Amine Oxidation and Imine Reduction 3 Addition Reactions of α-Amino Radicals 3.1 Conjugate Additions of α-Amino Radicals 3.2 Addition of α-Amino Radicals to Heteroaromatic Systems 3.3 Cross Coupling via Additions to Transition Metal Complexes 4 Radical Addition to C=N Bonds Using Photoredox Catalysis 4.1 Intramolecular Radical Addition to C=N Bonds 4.2 Intermolecular Radical Addition to C=N Bonds 5 Conclusion