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[PtCl₂{Te(CH₂)₆}₂] (<b>1</b>) was synthesized from the cyclic telluroether Te(CH₂)₆ and <i>cis</i>-[PtCl₂(NCPh)₂] in dichloromethane at room temperature under the exclusion of light. The crystal structure determination showed that in the solid state, <b>1</b> crystallizes as yellow plate-like crystals of the <i>cis</i>-isomer <b>1<i>_cis</i></b> and the orange-red interwoven needles of <b>1<i>_trans</i></b>. The crystals could be separated under the microscope. NMR experiments showed that upon dissolution of the crystals of <b>1<i>_cis</i></b> in CDCl₃, it isomerizes and forms a dynamic equilibrium with the <i>trans</i>-isomer <b>1<i>_trans</i></b> that becomes the predominant species. Small amounts of <i>cis-trans</i>-[Pt₃Cl₆{Te(CH₂)₆}₄] (<b>2</b>) and <i>cis</i>-<i>trans</i>-[Pt₄Cl₈{Te(CH₂)₆}₄] (<b>3</b>) were also formed and structurally characterized. Both compounds show rare bridging telluroether ligands and two different platinum coordination environments, one exhibiting a <i>cis</i>-Cl/<i>cis</i>-Te(CH₂)₆ arrangement and the other a <i>trans</i>-Cl/<i>trans</i>-Te(CH₂)₆ arrangement. Complex <b>2</b> has an open structure with two terminal and two bridging telluroether ligands, whereas complex <b>3</b> has a cyclic structure with four Te(CH₂)₆ bridging ligands. The bonding and formation of the complexes have been discussed through the use of DFT calculations combined with QTAIM analysis. The recrystallization of the mixture of the 1:1 reaction from <i>d</i>₆-DMSO afforded [PtCl₂{S(O)(CD₃)₂}{Te(CH₂)₆}] (<b>4</b>) that could also be characterized both structurally and spectroscopically.