In this work, self-combustion reactions (SCR) for the preparation of important cathode materials for rechargeable Li-ion batteries were investigated by thermal analytical tools (DSC, ARC, TGA), electron microscopy, XRD, various spectroscopies (MS, Raman, FTIR) and elemental analysis by ICP. The systems studied include solutions containing metal nitrates at the right stoichiometry and sucrose as a fuel, for the preparation of LiMn0.5Ni0.5O2 (layered), LiMn1.5Ni0.5O4 (spinel), LiMn0.33Ni0.33Co0.33O2 (layered), and LiMn0.4Ni0.4Co0.2O2 (layered). Similar products, which do not depend on the atmosphere of the processes (air or inert) were obtained by spontaneous SCR and the gradual heating of the same solutions by DSC, ARC, and TGA. The reactions involve the partial caramelization of sucrose, complicated by red-ox reactions with the nitrates that form solid products, whose organic part is finally decomposed around 400 °C. The presence of cobalt ions has a stabilizing effect, which is expressed by the low dissolution rates of Li ions from the solid products thus formed, into aqueous solutions. The reaction mechanisms are discussed herein. © 2009 Elsevier B.V. All rights reserved.