Lithium insertion mechanism in some antimony-based compounds: SnSb, CoSb3, CrSb2, TiSb2 has been studied by means of Sb-121 Mossbauer spectrometry which gives valuable information about the local electronic structure of the probed element (Sb). The structural and electronic modifications induced by insertion of lithium have been characterized. For these Sb-based materials the lithium insertion mechanisms involve Li3Sb formation and composite multi-phase separations with one component displaced from the pristine compound. (C) 2003 Elsevier Science B.V. All rights reserved.