Palladium(II) complexes with two thiophene derivatives bearing alkylsulfanyl chains, i.e., 3-(n-butylsulfanyl)thiophene and 4,4´-bis(n-butylsulfanyl)-2,2´-bithiophene, are synthesised and spectroscopically and electrochemically characterised. The molecular structure of PdCl2[3-(n-butylsulfanyl)thiophene]2 was determined by X-ray analysis. The properties of the complexes have been compared with those of PdCl2[3,3´-bis(n-butylsulfanyl)-2,2´-bithiophene] and of a conductive polymer partially coordinated with Pd(II), previously synthesised by us. We found that Pd(11) ions can coordinate sulfanyl sulfur atoms both in cis and trans configuration, leading to a reticulate material, where some kind of interchain bridging may be reasonably supposed to enhance the bulk conductivity.