To further advance metallaphotoredox C(sp 2 )-C(sp 3 ) cross-coupling, broaden its industrial applicability, and gain a better understanding of its mechanism, we reinvestigated the decarboxylative cross-coupling reaction of α-amino acids with aryl halides (Figure ). This reaction is desirable in medicinal chemistry because it uses abundant and cheap α-amino acids feedstock as diverse alkyl inputs. The optimization of the reported metallaphotoredox conditions resulted in the identification of a new set of conditions comprising of cheap and simple Ni catalyst system (H2O)6Ni(BF4)2 and bipyridine (bpy). Running the reaction in DMA and irradiating with violet-LEDs (λ = 400 nm) gave a higher yield of products compared to the combination of DMF and blue-LEDs (λ = 450 nm) used in the original report. With the use of new conditions, we were able to extend the scope to encompass αamino acids bearing pharmacophoric elements, which were previously unexplored coupling partners. α-amino acids bearing broad functional groups, including heterocycles, successfully underwent decarboxylative arylation with a diverse set of aryl bromides. Some intriguing observations that triggered new mechanistic investigations were made during the scope studies, namely: (i) proto-debromination and olefin sideproducts were observed in some reactions, and (ii) electronrich aryl bromides generally failed. Although beneficial effects have been observed in certain reactions, the inclusion of phthalimide as an additive in the reaction had little influence on the coupling with electron-rich arenes. Those observations prompted other questions about the accepted Ni(0)/Ni(II)/Ni(III)/Ni(I)/Ni(0) catalytic pathway, leading us to suspect that Ni could operate by an alternative pathway in this reaction. Results from experimental control reactions with Ni(II)-complexes, cyclic voltammetry (CV) and computational studies led us to propose an alternative mechanistic pathway for the decarboxylative arylation (Figure ). The dual-catalytic process begins with the SET oxidation of the carboxylate by the excited photocatalyst *Ir III (E1/2 red [*Ir III /Ir II ] = +1.21 V vs. SCE (Saturated Calomel Electrode) in CH3CN) to generate an α-amino radical after CO2 extrusion. Concurrent with the photoredox cycle, the oxidative addition of a Ni(0) species into the aryl halide would produce a Ni(II)ArBr intermediate. Distinct from previous proposals, the SET reduction of the Ni(II)ArBr complex (E1/2 red -1.25 to (-1.37) V vs. SCE in CH3CN depending on Ar substitution) by Ir II species (E1/2 red [Ir III /Ir II ] = -1.37 V vs. SCE in CH3CN) is thermodynamically feasible, forging a Ni(I)Ar species. The Ni(I)Ar species would rapidly intercept the α-amino radical, forming a Ni(II)Ar(R) adduct, which upon undergoing reductive elimination delivers the cross-coupled product with the concomitant release of Ni(0) species. Comprehensive Density Functional Theory (DFT) studies provide qualitative support for the viability of the Ni(I)Ar intermediate and suggest that the reductive elimination from Ni(II)Ar(R) intermediate is turnover limiting. In addition to undergoing reductive elimination, Ni(II)Ar(R) can also engage in a competitive β-hydride elimination resulting in proto-debromination and olefin sideproducts. While the previously discussed photochemical methodology and related work by MacMillan, Doyle, and others have proven effective at promoting C(sp 2 )-C(sp 3 ) from readily available carboxylic acids, key limitations hinder its broader utility in diverse drug discovery programs. First, the range of aryl coupling partners that perform well in decarboxylative cross-couplings is limited to electrondeficient arenes and heterocycles with few reports of electron-rich (hetero)arenes. Second, alkyl partners are generally limited to α-heteroatom carboxylic acids that generate stabilized radicals. Recently, MacMillan reported that the addition of phthalimide expands the substrate scope to include unactivated carboxylic acids. Notwithstanding, the intolerance of other functionalities such as electron-rich arenes and oxidizable tertiary amines presents a current substrate limitation of the photochemically driven process. In contrast, a reductive coupling approach driven by electricity should offer a solution to such challenges. During a terpene total synthesis campaign, Baran and coworkers discovered that the addition of silver nitrate to an electrochemically driven decarboxylative alkenylation reaction allowed for a chemoselective electron transfer to the Ni catalyst in the presence of other reductively labile functional groups. This additive led to expanded functional group tolerance and allowed for a streamlined series of natural product syntheses with minimal protecting groups. They postulated that silver nitrate in situ forms a silver nanoparticle (AgNP) layer on the cathode surface which protected against substrate and catalyst cathodic degradation. Taken together, our labs envisioned that such reactivity benefits from electrochemistry in the pursuit of linear terpenes could have a similarly significant impact on pharmaceutical synthesis (Figure ). Mechanistically, the electrochemically driven arylation with RAEs is distinct from that of photochemical arylation with acids. First, the silver nitrate is reduced to AgNP's that deposit on the cathode surface before the catalytic cycle begins. Then, Ni(II) is reduced to a low valent Ni(I) complex that undergoes oxidative addition to an aryl-halide to afford a Ni(III)-aryl(X)2 intermediate. Next, the Ni(III) species is reduced to a Ni(II)aryl(X) complex either by disproportionation with Ni(I) or through cathodic reduction. The Ni(II)-aryl(X) then captures an alkyl radical to form a Ni(III)-aryl(alkyl)(X) complex that undergoes reductive elimination to afford the desired aryl-alkyl product and a Ni(I)X species. The resulting Ni(I)X species can reduce the RAE through a SET to afford an alkyl radical while concomitantly producing a Ni(II) species that re-enters the catalytic cycle.