The methylation product of the reaction between [Pt₂(µ-S)₂(PPh₃)₄] and MeI in diethyl ether has been reinvestigated using positive-ion electrospray mass spectrometry and found to be contaminated with the dimethylated iodide-containing complex [Pt₂(µ-SMe)₂(PPh₃)₃I]⁺, which is believed to be formed early in the reaction. New, facile routes to the monomethylated complex [Pt₂(µ-S)(µ-SMe)(PPh₃)₄]⁺ have been developed using mild methylating agents. Heating [Pt₂(µ-S)₂(PPh₃)₄] in neat dimethyl methylphosphonate results in rapid and selective conversion to [Pt₂(µ-S)(µ-SMe)(PPh₃)₄]⁺; methylation with Me₃S⁺OH⁻ in refluxing methanol also affords pure [Pt₂(µ-S)(µ-SMe)(PPh₃)₄]⁺, isolated as its hexafluorophosphate salt. The X-ray structure of the previously reported complex [Pt₂(µ-SMe)₂(PPh₃)₂I₂] has also been undertaken.