A) Traditional Thermal Cross-Coupling Conditions It is to be noted here that tertiary amines, such as triethylamine and DABCO proved less effective under ligand-free photoredox reaction conditions compared to primary amines. For instance, triethylamine led to the formation of the protodehalogenated product, likely due to its role as a sacrificial electron donor in photoredox conditions (Table , entry 1). DABCO, despite being more nucleophilic and expensive, failed to facilitate the desired cross-coupling reaction efficiently (Table , entry 2). Hexylamine, a primary amine, underwent self-coupling, yielding mono-and diarylated anilines (Table , entry 3). Similarly, cyclohexylamine and isopropylamine exhibited self-coupling to the monoarylation product. A significant improvement was observed with an increase in steric profile: the use of 1-adamantylamine and tert-butylamine enabled highly efficient phenol cross-coupling at room temperature, achieving excellent yields of 91% and 94%, respectively. The exceptional performance of tert-butylamine in nickel-photoredox cross-coupling reactions is particularly noteworthy (additive evaluation for other nucleophiles see Figure and S4, Table and). The tertiary alkyl group in tert-butylamine enhances coordination lability, facilitating efficient ligand exchange and turnover. Additionally, the increased size makes reductive elimination and self-coupling more challenging, while minimizing undesired reductive byproduct formation due to the absence of α-hydrogen atoms. Importantly, the primary amino group in tert-butylamine maintains sufficient donor capacity to ensure nickel's reactivity in the oxidative addition event. Control experiments, in which light, 4CzIPN (as a photocatalyst), or NiBr₂•glyme were omitted, confirmed the necessity of all components for efficient cross-coupling reactions (Table ).