Nature Chemistry, Published online: 10 June 2026; doi:10.1038/s41557-026-02177-8 Selective radical capture remains a central challenge in transition metal-catalysed transformations involving multiple radical intermediates. Now a ligand-modulated metal–radical polarity-match mechanism exploiting electronic bias for selective radical capture has been identified. This principle enables general photoredox/copper-catalysed 1,2-dicarbofunctionalization of ethylene, providing modular access to structur