The molecular dynamics computer simulation technique was used to evaluate the early stages of Li ion migration occurring at the electrolyte/cathode interface applicable to solid-state oxide thin film batteries. A V2O5 crystal was oriented such that its (001) planes were parallel to the lithium metasilicate glass surface, and intercalation of lithium ions from the glass into the crystal in the <001> direction was simulated. During the simulation, a transformation of the V2O5 crystal to delta-LiV2O5 was observed. This transformation occurred in a layer-by-layer manner dependent on the presence of the Li ions between the transforming (001) crystal planes. The simulation also showed the lithium ions having better mobility between the layers than across the layers.