alpha-MnSe thin films have been prepared by reactive pulsed laser deposition. The physical and electrochemical properties of the as-deposited thin films firstly have been investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), and selected area electron diffraction (SAED), as well as galvanostatic cycling and cyclic voltammetry (CV). Discharge capacities in the ranges from 361 to 472 mAh g(-1) were achieved during the first 120 cycles. By using ex situ XRD and SAED measurements, the electrochemical reaction mechanism of alpha-MnSe thin films with lithium upon cycling involving the irreversible decomposition of a-MnSe and reversible formation of beta-MnSe was proposed. (c) 2007 Elsevier B.V. All rights reserved.