We have investigated the reaction mechanisms occurring upon the first discharge/charge cycle of a MnSn2//Li electrochemical cell, by using bulk- and surface-sensitive characterization techniques (Xray Diffraction, Sn-119 Mossbauer spectroscopy, magnetic measurements, X-ray photoelectron and Auger spectroscopies). Compared to other tin-transition metal alloys, MnSn2 displays an original behaviour. Lithium insertion into MnSn2 particles results in a nanocomposite consisting of Li7Sn2 phase, and of Mn nanoparticles which are immediately oxidized at their surface. Lithium extraction from this nanocomposite leads to the formation of magnetic MnSn2 particles and to our knowledge it is the first time such a mechanism is observed in tin-based intermetallic electrode materials due to electrochemical reaction with Li. The solid electrolyte interphase (SEI) is formed at the beginning of the first discharge and its thickness slightly increases upon further lithium insertion. A partial re-dissolution process occurs upon lithium extraction from the material, while its chemical composition is very stable over the whole cycle. (C) 2014 Elsevier Ltd. All rights reserved.