The reaction of [PdCl(E^∩N)]n with AgOAc in methanol afforded the corresponding acetato complexes, [Pd(OAc)(E^∩N)]_n (E^∩N/n = ECH₂CH₂NMe₂/3; ECH2CH2CH2NMe₂/2 (E = S or Se)). The molecular structures of [Pd(OAc)(ECH₂CH₂NMe₂)]₃ were established by single crystal X-ray diffraction analyses. The trimeric structures comprise of three palladium atoms bridged through chalcogen atoms of the chelating chalcogenolate ligand forming a twisted six-membered Pd₃E₃ ring. The acetato-ligand acts in a monodentate fashion. The catalytic activity of [PdCl(E^∩N)]n and [Pd(OAc)(E^∩N)]n in Suzuki CeC cross coupling reactions has been investigated. The dimeric acetato complexes showed the best activity in dioxane.