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We report the synthesis and characterisation of a series of siloxide-functionalised polyoxovanadate–alkoxide (POV–alkoxide) clusters, [V 6 O 6 (OSiMe 3 )(OMe) 12 ] n ( n = 1−, 2−), that serve as molecular models for proton and hydrogen-atom uptake in vanadium dioxide, respectively. Installation of a siloxide moiety on the surface of the Lindqvist core was accomplished via addition of trimethylsilyl trifluoromethylsulfonate to the fully-oxygenated cluster [V 6 O 7 (OMe) 12 ] 2− . Characterisation of [V 6 O 6 (OSiMe 3 )(OMe) 12 ] 1− by X-ray photoelectron spectroscopy reveals that the incorporation of the siloxide group does not result in charge separation within the hexavanadate assembly, an observation that contrasts directly with the behavior of clusters bearing substitutional dopants. The reduced assembly, [V 6 O 6 (OSiMe 3 )(OMe) 12 ] 2− , provides an isoelectronic model for H-doped VO 2 , with a vanadium( iii ) ion embedded within the cluster core. Notably, structural analysis of [V 6 O 6 (OSiMe 3 )(OMe) 12 ] 2− reveals bond perturbations at the siloxide-functionalised vanadium centre that resemble those invoked upon H-atom uptake in VO 2 through ab initio calculations. Our results offer atomically precise insight into the local structural and electronic consequences of the installation of hydrogen-atom-like dopants in VO 2 , and challenge current perspectives of the operative mechanism of electron–proton co-doping in these materials.