AbstractMagnesium batteries attract interest as alternative energy‐storage devices because of elemental abundance and potential for high energy density. Development is limited by the absence of suitable cathodes, associated with poor diffusion kinetics resulting from strong interactions between Mg²⁺ and the host structure. V₂PS₁₀ is reported as a positive electrode material for rechargeable magnesium batteries. Cyclable capacity of 100 mAh g⁻¹ is achieved with fast Mg²⁺ diffusion of 7.2 10⁻¹¹–4 10⁻¹⁴ cm² s⁻¹. The fast insertion mechanism results from combined cationic redox on the V site and anionic redox on the (S₂)²⁻ site; enabled by reversible cleavage of S−S bonds, identified by X‐ray photoelectron and X‐ray absorption spectroscopy. Detailed structural characterisation with maximum entropy method analysis, supported by density functional theory and projected density of states analysis, reveals that the sulphur species involved in anion redox are not connected to the transition metal centres, spatially separating the two redox processes. This facilitates fast and reversible Mg insertion in which the nature of the redox process depends on the cation insertion site, creating a synergy between the occupancy of specific Mg sites and the location of the electrons transferred.