This work presents an investigation of the multifunctional alkylation chemistry of the metalloligand [Pt2(µ-S)2(PPh3)4]. [Pt2(µ-S)2(PPh3)4] is known to be one of the best building block for multimetallic molecules through the exceptional ligating ability of the two sulfide centres to virtually any transition and main group metal fragment. Extension of the synthetic versatility of [Pt2(µ-S)2(PPh3)4] to multifunctional non-metallic positive centres was explored in this work. By using Electrospray Ionisation Mass Spectrometry (ESI-MS) as the main monitoring tool, [Pt2(µ-S)2(PPh3)4] was employed as a productive template for generating structurally and chemically diverse thiolate-platinum complexes. Multifunctional organic groups which include semi- and thiosemicarbazone, urea, isocyanate, guanidine, ketones, amines, amides and polymers with suitable electrophilic branches reacts with [Pt2(µ-S)2(PPh3)4] by alkylation of one or both sulfide centres to generate the corresponding functionalised derivatives containing thiolate ligands bonded to platinum.