A series of novel platinum(II) acetylide complexes incorporating sulfur-linked oligoalkynes have been prepared. The CuI-catalysed dehydrohalogenation reactions of the mono-protected dialkyne ligand HCCSCC(TIPS) (TIPS = Prⁱ₃Si) with trans-[Pt(PBu₃)₂Cl₂], cis-[Pt(dppe)Cl₂] or cis-[Pt(Me₂bipy)Cl₂] (Me₂bipy = 4,4′-dimethyl-2,2′-bipyridine), in the presence of a base, readily produced trans-[Pt(PBu₃)₂{CCSCC(TIPS)}₂] 1, cis-[Pt(dppe){CCSCC(TIPS)}₂] 3 and cis-[Pt(Me₂bipy){CCSCC(TIPS)}₂] 7, respectively, in good yields. Similar synthetic procedures using a diacetylenic sulfide species HCCSCCCCSCC(TIPS) afforded trans-[Pt(PBu₃)₂{CCSCCCCSCC(TIPS)}₂] 2 and cis-[Pt(dppe){CCSCCCCSCC(TIPS)}₂] 4, both of which contain eight triple-bond units within the molecular entity. Two new metallo-end-capped derivatives trans-[Ph(Et₃P)₂Pt–CCSCC–Pt(PEt₃)₂Ph] 5 and trans-[Ph(Et₃P)₂Pt–CCSCCCCSCC–Pt(PEt₃)₂Ph] 6 were also synthesized in moderate yields by reactions of two equivalents of trans-[PtPh(Cl)(PEt₃)₂] and the diterminal acetylenic sulfides HCCSCCH and HCCSCCCCSCCH in a CuI/(Me₃Si)₂NH system. All of the compounds 1–7 have been characterized by IR, NMR (¹H, ¹³C and ³¹P) and UV/VIS spectroscopies, luminescence measurements and mass spectrometry. The solid-state molecular structures of 5 and 7 have been established by X-ray crystallography.