Accelerating rate calorimetry (ARC) and differential scanning calorimetry (DSC) were used to study the thermal behaviour of a commercially available lithium-ion cell. Both the complete cell (pouch type, 2 Ah) and its electrode materials, respectively, were investigated. As positive electrode material a blend system consisting of NCM (=Li[Ni0.33Co0.33Mn0.33]O2) and LMO (=LiMn2O4) with a weight ratio of 4:1 was identified. The main exothermic behaviour is dominated by the positive electrode–electrolyte reaction. ARC studies on the positive electrode material in presence of our reference electrolyte show an inhibiting effect of the conducting salt LiPF6 towards the oxidation of the organic based electrolyte by released oxygen. X-ray diffraction measurements were performed to study the thermal decomposition behaviour of the positive active material. Both the blend system and the single components, NCM and LMO, were investigated at different temperatures. A significant phase transformation from the hexagonal layered to a cubic structure as well as various reduction products could be identified. Finally, the thermal behaviour of the NCM/LMO-blend and its single phases, NCM and LMO, at different states of charge (SOC) was investigated. Therefore, detailed investigations based on differential scanning calorimetry (DSC) and cyclic voltammetry (CV) were performed.