Persistent transition metal radicals form the foundation for many metallaphotoredox protocols. Their ability to efficiently trap organic radicals and convert them into various coupling products has inspired the exploration of selective radical reactions even beyond the d-block. Radical processes involving bismuth hold great potential but innovative strategies are required to control the reactivity of bismuth intermediates. Herein we report preassembly as a powerful strategy to enforce a selective recombination of a bismuth(II) radical and an organic radical. As a result, an inner-sphere pathway is accessed, enabling the formation of C–N coupling products.