In this work the electrochemical behavior of α-V2O5 at RT, in a 1M NaClO4/PC (propylene carbonate) electrolyte is investigated for the first time. The irreversible formation of a sodiated layered compound is shown from the first electrochemical discharge step. This electrochemically formed compound, with highly stable structure close to that of the high temperature α’-NaV2O5 orthorhombic bronze, is demonstrated to be a genuine sodium intercalation compound. This material exhibits a high capacity of 120mAhg−1 available near 1.6V at C/10 rate with a promising cycling behaviour. X-ray diffraction and Raman spectroscopy show zero strain structural behaviour during Na+ insertion/extraction in this large interlayer spacing material.