Ag2Se thin film has successfully been fabricated by pulsed-laser deposition method. X-ray diffraction (XRD) measurement indicated that the as-deposited Ag2Se thin film consisted mainly of orthorhombic β-Ag2Se. A reversible electrochemical reaction of Li/Ag2Se cell has been investigated by discharge–charge and cyclic voltammetry (CV) measurements for the first time. The reversible capacity of Ag2Se electrode exhibited more than 5.6 Li per Ag2Se at 10μA/cm2. Both alloying/de-alloying processes and selenidation/reduction processes of Ag were revealed during the lithium electrochemical reaction of Ag2Se thin film electrode. Ag2Se was found to be one novel candidate of anode materials for rechargeable lithium batteries.