The conductivity change of a vacuum deposited V2O5 thin film during lithium intercalation/deintercalation was investigated using an interdigitated microarray electrode. The conductivity-potential profile showed two peaks (ca. 1.7 × 10−3 S cm−1) at 3.23 V and 3.41 V vs. Li/Li+, corresponding to the peaks in the cyclic voltammogram for Li intercalation/deintercalation. The conductivity decreased below 10−5 S cm−1 when the potential was scanned to the region more negative than 3.0 V vs. Li/Li+ and an irreversible conductivity change was observed when the potential was scanned back.