Nanostructured bilayered V2O5 was electrochemically deposited within carbon nanofoam conductive support. As prepared electrochemically-synthesized bilayered V2O5 incorporates structural water and hydroxyl groups that effectively stabilizes the interlayers and provides coordinative preference to the Mg(2+) cation in reversible cycling. This open framework electrode shows reversible intercalation/deintercalation of Mg(2+) ions in the common electrolytes such as acetonitrile. Using scanning transmission electron microscope we demonstrate that Mg(2+) ions can be effectively intercalated into interlayer spacing of nanostructured V2O5, enabling electrochemical magnesiation against Mg anode with near theoretical specific capacity of 240 mAh/g. We employ HRTEM and x-ray fluorescence (XRF) imaging to understand the role of environment in the intercalation processes. A rebuilt full cell was tested by employing a high-energy ball milled Sn alloy anode in acetonitrile with Mg(ClO4)2 salt. XRF microscopy reveals effective insertion of Mg ions throughout the V2O5 structure during discharge, and removal of Mg ions during electrode charging in agreement with electrode capacity. We show using XANES and XRF microscopy that reversible Mg intercalation is limited by the anode capacity.