The solid electrolyte interphase (SEI) layer on AlSb electrodes has been studied in Li/AlSb cells containing a LiPF6 EC/DEC electrolyte using X-ray photoelectron spectroscopy (XPS). Data were collected before SEI-formation, during formation, and after formation at 0.01 V versus Li-0/Li+, and at full delithiation in cycled cells at 1.20V. The thickness of the SEI layer increases during lithiation and decreases during delithiation. This dynamic behaviour occurs continuously on cycling the cells. The growth of the SEI layer can be attributed predominantly to the deposition of carbonaceous species below 0.50 V versus Li-0/Li+; these species disappear almost completely during delithiation. The extra surface-layer formation is a consequence of the additional charge that is needed to lithiate the remaining Sb component of the micrometer-sized AlSb particles at low potentials as seen by synchrotron-based X-ray diffraction. Aluminium is not reactive to lithium alloying in this electrolyte. Relatively small amounts of LiF were detected in the AlSb SEI layers compared to that commonly found in the SEI layers on graphite electrodes. (c) 2007 Elsevier Ltd. All rights reserved.