In conclusion, we report a general cross-coupling protocol employing tert-butylamine as a dual-function additive, marking a significant advancement in nickel-catalyzed photoredox chemistry. This method simplifies reaction conditions with good efficiency, demonstrating broad applicability across various nucleophiles and electrophiles, including biomolecules. Tertbutylamine effectively serves as both a ligand and a base, addressing common challenges associated with traditional bases and ligands, such as solubility issues and the need for specific optimization. Additionally, simple and interpretable structureactivity relationships provide a foundation for more sophisticated data science models and enable qualitative estimation of reaction outcomes. The compatibility of various nucleophiles allow sequential one-pot difunctionalizations, showcasing its practicality for constructing molecular complexity and rapid compound library generation. The homogeneous and precipitatefree nature of the system with cost-effective reagents facilitates convenient scaling to gram quantities and promises applicability in larger-scale processes using flow technology.