Vanadium pentoxide xerogel films intercalated by poly (ethylene oxide), PEO, were prepared using direct intercalation method via a sol-gel route. The electrical and electrochromic characterization of the films were conducted. The electrical properties along and across V-O layers have been evaluated. The results indicate that the proper amount of PEO can increase the electrical conductivity and charge density of the films. The electrochromism of the films upon lithium intercalation was investigated by ex-situ transmittance measurement. The films display a reversible multichromism (orange green blue) upon Li+ ion insertion/extraction.