Interestingly, when subjected to the conditions outlined in their study, we successfully obtained product 46 with a yield of 63%. This consecutive transformation highlights the orthogonal nature of these two approaches. the presence of the photocatalyst and light, reactivity was restored, yielding a 77% 1 H-NMR yield of product 3. Furthermore, in a stoichiometric experiment, where 1 equivalent of the oxidative addition complex Ar-Ni II -Br was stirred in the dark without photocatalyst for 3 hours, a 42% 1 H-NMR yield of compound 3 was obtained. When substrate 1n was subjected to our optimized conditions, we detected traces of a product resulting from chain-walking via reiterated β-hydride elimination and migratory insertion (compound 47γ). Notably, when ligand L2, known to promote chain-walking, was employed, selectivity was completely shifted towards the benzylic position (Scheme 4D). This observation supports our proposal that chain-walking occurs prior to reductive elimination, aligning well with the control experiments mentioned earlier. Taken together, these experiments provide evidence that the photocatalytic system plays a crucial role in enhancing nickel catalysis, likely by accelerating the reductive elimination step. To further explore the reaction kinetics, we conducted an investigation into the dependence of the initial rate on various factors, including substrate concentration, nickel catalyst concentration, and base concentration in the reaction between 1a and 2a. The progress of the reaction and the formation of product 3 were monitored using 1 H-NMR. This study revealed that, under the optimized conditions, the reaction operates in a photon-limited regime, indicating that the rate is primarily determined by the availability of photons. Intriguingly, the reaction exhibited zeroth order kinetics with respect to all other reaction components. A related Hammett plot supported the conclusion of a photon-limited regime (see Section 6.3 Supplementary Information). It is worth noting that the rate-limiting step shifted to oxidative addition only in the case of electron-rich aryl bromides, such as 4-bromoanisole.