In summary, we have disclosed a visible-light-mediated three component Ritter-type olefin carboamidation using readily accessible carboxylic acid-derived redox-active esters. In this study, using the organophotocatalyst 4-CzIPN, we successfully (i) tamed previously unexplored decarboxylative-generated nucleophilic primary radicals, enabling their incorporation in the three-component process with styrenes and nitriles, and (ii) developed a general retrosynthetic disconnection strategy to rapidly increase molecular complexity, offering a novel route to amidated precursors for the synthesis of pharmaceutically relevant scaffolds. Furthermore, a serendipitous chemodivergence has been explored when 1,1-diarylolefins were utilized as reaction partners, leading to the development of a straightforward and additive-free photocatalytic Heck-type reaction methodology. Both transformations demonstrated good functional group tolerance with respect to aryl olefins and redox-active esters, resulting in broad applicability. Scalability in both batch and continuous-flow processes has demonstrated the effectiveness and the synthetic utility of the presented protocols.