The ruthenium(II) complex [Ru([14]aneS4)(bpym)](BF4)2 ([14]aneS4=1,4,8,11-tetrathiacyclotetradecane, bpym=2,2′-bipyrimidine) has been prepared by substitution of the labile acetonitrile ligands in the complex [Ru([14]aneS4)(CH3CN)2](BF4)2 by bpym. Both the precursor acetonitrile complex and the polypyridyl complex were characterised by Ru K-edge EXAFS spectroscopy. In addition, the crystal structures of [Ru([14]aneS4)(bpym)](X)2 (X=BF4, PF6) were determined by X-ray diffraction. The bpym-bridged bimetallic complexes [{Ru([14]aneS4)}2(bpym)](BF4)4 and [{([14]aneS4)Ru}(bpym){ReO3Me}](BF4)2 were prepared using the ruthenium(II) monomeric bpym complex as starting material. In the case of the complex containing methyltrioxorhenium(VII) coordination of both metal centres to the bidentate bridging ligand was supported by a combination of Ru K-edge and Re L-edge XAFS spectroscopy, in addition to 1H NMR.