In conclusion, we report a novel photolytic Nickel-catalyzed decarboxylative dehydrogenation toward (Z)-enamides using natural and non-natural amino acid starting materials. This transformation is reinforced by modulating the electronic and steric properties of nickel intermediates with aryl halides additives. Additionally, the introduction of ortho-substituents significantly enhances β-H abstraction due to diminished reductive elimination kinetics. A novel photoredox catalyst (Ir-3) has been carefully designed, incorporating the capability of performing SET and EnT in the same reaction mixture for obtaining stereoselective enamides. Ultimately, we have successfully performed the synthesis of diversely functionalized arylated (Z)-enamides in up to excellent yields and selectivity. The mechanistic details, in particular with regards to the steric effects of this methodology on the nickel catalytic cycle were elucidated and are currently under further investigation in our laboratory. The careful modulation of redox states of nickel catalysts will enable the design and development of new catalytic reactivities in the future.