The self-assembly of 4,4′-dipyridylditelluride/diselenide and M(OTf )₂ {M = cis-[Pt(PEt₃)₂]²⁺ or cis-[Pd(dppe)]²⁺; dppe = 1,2-bis(diphenylphosphino)ethane} yields [M(μ₂-4,4′- py₂E₂)]_n(OTf )_2n (E = Se, Te). The major and minor products, indistinguishable by simple proton NMR and phosphorus NMR spectroscopy, can be detected by heteronuclear (⁷⁷Se, ¹²⁵Te, and ¹⁹⁵Pt) NMR spectroscopy. The respective dimeric and tri-meric structures are assigned by ESI and MALDI-TOF mass spectrometry, and for the first time, their equilibria have been established. The rhomboid shape of the dimeric complex containing the Pt–N bond is confirmed by its X-ray diffraction structure. The formation of the cluster-type minor product [Pd₃(μ-E)₂-(dppe)₃](OTf )₂ has also been identified in the reactions of the Pd complexes.