Nitrogen-containing organic compounds are prevalent in natural and pharmaceutical relevant motifs, with over 90% of drug molecules market incorporating nitrogen atoms. Given this significance, the development of strategies for C-N bond formation is of critical importance. Within this area, the Ritter reaction offers a straightforward approach for synthetic chemists, harnessing alkene-or alcohol-derived carbocations and nitriles. Since its inception in 1948, the Ritter reaction has undergone continuous development towards greener conditions and to broaden its precursor pool. Notably, the advent of oxidative radical-polar crossover (RPC), which sequentially exploits the reactivity of radicals and cations, has enabled the integration of the Ritter-type process into atom and step-economical multicomponent reactions (MCRs). In this regard, threecomponent alkene difunctionalizations represent a hot topic nowadays as (i) olefins are inexpensive and readily available organic feedstocks, and (ii) the introduction of two new, orthogonal functionalities into the C=C bond results in a rapid increase in molecular complexity, enhancing sp³ character and thereby contributing to the "Escape from Flatland" strategy in drug discovery. In recent years, various alkene difunctionalization protocols have incorporated the Ritter-type amidation as the final step to trap the carbocation, generated via Giesetype addition and RPC of the radical intermediate, starting from both heteroatomic-(N, O, P and S) and carbon-centered radical precursors. Regarding the latter, CF3 and aryl moieties insertions are well-established using the Umemoto reagent or analogues and diazonium salts, respectively. In the realm of alkene carboamidations, alkyl radicals can be generated via thermal processes (50-80 °C) from diacyl peroxide reactants in the presence of an iron catalyst or by activating the C(sp )-H bond of alkane reactants using benzoyl peroxide and radical initiators (Figure ). Building on these findings, the groups of Chen and Maity reported photoredox-catalyzed carboamidation protocols using α-bromo nitriles, ketones and esters as radical precursors (Figure ). Noteworthy in these reports are the use of cost-effective starting materials along with additives (KF or Zn(OAc)2) that completely suppress alkylbromination by-products resulting from atom transfer radical addition (ATRA). However, these conditions depend on electrophilic α-cyano and keto/ester primary radicals, thus limiting the generality of the approach. In light of this, a photocatalytic complementary strategy that can harness non-stabilized nucleophilic radicals is highly desirable. With this target in mind and inspired by a recent netoxidative photoelectrochemical Ritter-type protocol disclosed by our group, a redox-neutral photocatalytic single electron transfer (SET) approach was envisioned starting from readilyaccessible carboxylic acids activated as N-hydroxyphthalimide (NHPI)-based redox-active esters (RAEs), offering an intuitive retrosynthetic strategy. In fact, due to their stability and ease of preparation, NHPI esters constitute the dominant choice as alkylating agents in decarboxylative three-component styrene difunctionalizations, as demonstrated in examples with oxygen-(water, alcohols), nitrogen-(amides, amines), carbon-(cyano, indoles) or halogen-(Cl, F) based nucleophiles. However, a crucial remaining challenge in MCRs lies in the use of primary radicals, as previous protocols were generally limited to secondary and tertiary precursors. Herein, we report the achievement of highly reactive primary alkyl radicals for tandem RPC Ritter-type process by leveraging an organophotocatalyst under visible light irradiation (Figure ). Furthermore, during the realization of this protocol, it was found that Heck-type products were chemoselectively obtained by simply switching aryl olefin Giese-type acceptors with 1,1diarylolefins (cf. Table , vide infra). Thus, a transition metaland additive-free alkenylation of carbon-centered radicals was optimized and applied to synthesize various trisubstituted alkenes. Our unifying chemodivergent strategy proved applicable to late-stage functionalization (LSF) of relevant scaffolds and was efficiently scalable in both batch and continuous flow (up to a gram/multi-mmol scale).