Enamides, known for their versatility in organic synthesis, represent important motifs in complex natural products (Figure ), pharmaceuticals, as well as intermediates for successive functionalization. Common transition metal catalytic syntheses utilize palladium catalyzed decarbonylative elimination, reductive acylation of oximes by iron, coppercatalyzed amidation of vinyl halides, nickel-mediated decarbonylation of amino acid thioester, and rutheniumpromoted anti-Markovnikow hydroamination of terminal alkynes (Figure 1B, left). However, a broadly applicable methods, favoring the (Z)-products, operating at ambient conditions and starting from renewable resources and naturally abundant transition metals would be highly desirable. Metallaphotoredox catalysis, which has greatly expanded the capacities of traditional cross-coupling reactions, enables the conversion of naturally abundant fatty or amino acids into target molecules under mild blue light conditions. The combination of an initial decarboxylation event with subsequent metal-catalyzed elimination or dehydrogenation would be an effective strategy achieving the desired enamide products. Seminal photocatalytic studies by Glorius and Ritter employed the decarboxylative elimination or dehydrogenation of amino or aliphatic carboxylic acids. On the one hand, Glorius' group reported a photocatalytic dehydro-decarboxylation of redox-active esters utilizing Cu catalysis merged with an organic dihydrophenazine photocatalyst. On the other hand, Ritter's group reported the combination of Co and Ir photoredox catalysis to obtain terminal olefins. In related studies, Tunge et al. employed Cu or Co catalysis for hydrogen atom transfer (HAT) merged with organic (acridinium) photocatalysts and achieved enamides from amino acid (Figure , right). Enamide products were obtained in good yields with moderate (E):(Z) ratios. Additionally, the groups of Larionov, König, as well as Wang and Chen developed strategies to obtain enamides or enamines with the help of photocatalysis. Most noteworthy, König's group introduced a Ni and Ir catalytic system capable of facilitating a formal β-hydride elimination, which was promoted by bromine radical formation and subsequent HAT, producing cyclic products in high yields. Despite these seminal contributions, the highly (Z)-selective synthesis of enamides remains challenging and arylated motifs as well as trifunctionalized olefins remain inaccessible. To this end, we were wondering whether (Z)-enamines can be obtained by an initial Ir-photocatalyzed decarboxylation utilizing natural or non-natural amino acids as abundant starting materials. An Ir photocatalysts with an appropriate redox window for efficient initial decarboxylation will lead to the formation of carboncentered radicals, which readily engage with nickel catalysts (Figure ). In the presence of aryl halides, nickel(III) intermediates are formed, which could be reduced if long-lived, facilitating the β-H elimination step. Kochi observed that orthosubstituents on aryl halides hamper the reductive elimination in Ni-catalyzed cross-coupling reactions. Likewise, Percec studied Ni-catalyzed homo-polymerization and found a decrease in yield when ortho-substituents were present and more recently Doyle detected sluggish oxidative addition kinetics of 2bromotoluene. Based on these seminal reports we argue that such an ortho-effect would be a powerful design criteria in our hands for redox-modulation of Ni(III) intermediates and thus outcompeting reductive elimination with β-H elimination. Subsequently triplet energy transfer from the very same Ir photocatalyst leads to distinct (Z)-selectivity of enamide products based on highly efficient photo-isomerization. In this report we successfully achieved the (Z)-selective synthesis of enamides via a new nickel photocatalytic strategy merged with single electron transfer (SET) and energy transfer catalysis simultaneously. Moreover, we could expand this reactivity to the synthesis of aliphatic and aromatic carbonyl compounds.