CuInSe2 thin films were fabricated by pulsed laser deposition and its electrochemistry with lithium was investigated. The reversible discharge capacity of the CuInSe2/Li cell cycled between 0.01 V and 2.5 V was found to be in the range of 438 to 647 mAh g(-1) during the first 100 cycles. By using ex situ X-ray diffraction, transmission electron microscopy, selected-area electron diffraction measurements and X-ray photoelectron spectroscopy, both classical alloying process and separated selenization/reduction of nanosized metallic In and Cu were proposed for the lithium electrochemical reaction of CuInSe2. indicating one of the features of the lithium electrochemistry of CuInSe2. CuInSe2 has high reversible capacity and good cycle performance, which makes it potential anode material for future lithium-ion batteries. (C) 2008 Elsevier B.V. All rights reserved.