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The palladium-catalyzed sp-sp2 C−C bond forming the Sonogashira reaction has been both extensively studied mechanistically and widely used in organic synthesis. Herein, we describe an investigation into how a palladium(II) complex with arylazoformamide (AAF) ligands mediates these transformations. When mixed, two AAFs coordinate in a κ1-fashion with an equivalent of PdCl2, creating complexes of the form PdCl2(AAF)2. Under typical and optimized copper(I)-cocatalyzed Sonogashira conditions, using phenylacetylene and iodobenzene as reagents, these complexes (precatalysts) reduce to Pd(0) and afford the coupled diphenylacetylene product in high yields (i.e., 99%). A substrate scope explored the substitution on both rings, yielding 18 examples with yields varying from 38 to 99%. Mechanistically, from DFT studies, a formal Pd(I) open-shell singlet complex is suggested, along with an explanation of the need for DBU when employing CuI in toluene. Further DFT exploration provides insight into the copper-free Sonogashira reaction when utilizing Pd(AAF)2 complexes.