The chiral compound (2-Me2NCH2C6H4)PhSbCl (1) was obtained from (2-Me2NCH2C6H4)Li and PhSbCl2 in 1 : 1 molar ratio, while (2-Me2NCH2C6H4)Mes2Sb (2) was prepared from (2-Me2NCH2C6H4)SbCl2 and MesMgBr in 1 : 2 molar ratio. The compounds 1 and 2 were used to obtain the Pd(II)/stibine complexes: [Me2NHCH2C6H5]+[PdCl3{SbCl(Ph)(C6H4CH2NMe2-2)-Sb}]− (3) and [PdCl2{SbMes2(C6H4CH2NMe2-2)-N,Sb}] (4). All the compounds were characterized by multinuclear NMR spectroscopy in solution, elemental analysis, mass spectrometry and single-crystal X-ray diffraction studies. In compounds 1–3 the coordination geometry around the antimony atom is pseudo-trigonal bipyramidal, while in compound 4 a tetrahedral geometry around the antimony atom is observed. Theoretical calculations at the DFT level on compounds 1–4 were used in order to gain insight into the nature of the coordinative bonds.