Recycling of Li-Ion Batteries (LIBs) is still a topic of scientific interest. Commonly, spent LIBs are pretreated by mechanical and/or thermal processing. Valuable elements are then recycled via pyrometallurgy and/or hydrometallurgy. Among the thermal treatments, pyrolysis is the most commonly used pre-treatment process. This work compares the treatment of typical cathode nickel-cobalt-aluminum (NCA) material by conventional pyrolysis, and by a microwave assisted pyrolysis. In the conventional route, the heating is provided indirectly, while via microwave the heating is absorbed by the microwaves, according to the materials properties. The comparison is done with help of a detailed characterization of solid as well as the gaseous products during and after the thermal treatment. The results indicated at least three common stages in the degradation: Dehydration and evaporation of electrolyte solvents (EC) and two degradation periods of EC driven by combustion and reforming reactions. In addition, microwave assisted pyrolysis promotes catalytic steam and dry reforming reactions, leading to the strong formation of H₂ and CO.