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The reaction of sulfur ylides (L) SMe2C(H)C(O)R (R = 4-nitrophenyl, phenyl, and 3-nitrophenyl) with the dichloro(1,5-cyclooctadiene)palladium(II) complex, [PdCl2(cod)], in a 2 : 1 ratio gives the new Pd(II) complexes of type cis- and trans-[PdCl2(SMe2C(H)C(O)R)2] (R = phenyl (1), 3-nitrophenyl (2), and 4-nitrophenyl (3)). Characterization of the obtained complexes was performed by elemental analysis, IR, 1H, 13C NMR and mass spectroscopies. Also, the structure of complex trans-[PdCl2(SMe2C(H)C(O)C6H4-p-NO2)2] (3) was characterized by single crystal X-ray analysis. The X-ray crystallography results reveal that the structure of complex 3 contains two Cα-coordinated sulfur ylide ligands in trans geometry. These air/moisture stable complexes were also employed as efficient catalysts for the Mizoroki–Heck cross-coupling reaction of several aryl halides with olefins. The coupled products of these reactions …