V2O5 is of interest as a Mg intercalation electrode material for Mg batteries, both in its thermodynamically stable layered polymorph (α-V2O5) and in its metastable tunnel structure (ζ-V2O5). However, such oxide cathodes typically display poor Mg insertion/removal kinetics, with large voltage hysteresis. Herein, we report the synthesis and evaluation of nanosized (ca. 100 nm) ζ-V2O5 in Mg-ion cells, which displays significantly enhanced electrochemical kinetics compared to microsized ζ-V2O5. This effect results in a significant boost in stable discharge capacity (130 mA h g−1) compared to bulk ζ-V2O5 (70 mA h g−1), with reduced voltage hysteresis (1.0 V compared to 1.4 V). This study reveals significant advancements in the use of ζ-V2O5 for Mg-based energy storage and yields a better understanding of the kinetic limiting factors for reversible magnesiation reactions into such phases