Cashew nut shells (CNS) are an abundant agricultural byproduct in West Africa but remain little or not valorized into energy due to the presence of extractives known as Cashew Nut Shell Liquid (CNSL). These extractives, which can constitute up to 40% of CNS, pose challenges for thermochemical conversion. This work investigates the behavior during the pyrolysis of the main CNSL components, i.e. anacardic acids, cardanols, and cardols (ACC), with the objective of determining their thermal degradation mechanisms. Thermogravimetric (TG) experiments were conducted, with interruptions at various pre-selected temperatures to collect samples and analyze the 12 isomers remaining in the residual ACC. Results showed that the ACC degradation mechanisms involve several main reactions: decarboxylation of anacardic acids, polymerization and cracking of cardanols and cardols as well as thermal degradation of cardanol- and cardol-based polymers. A competitive behavior between polymerization and cracking reactions, dependent on the sample mass was observed. The thermal behavior of cardanols and cardols was also shown to be influenced by sample size, with larger samples promoting polymerization due to increased intermolecular interactions, while smaller samples favored cracking reactions by facilitating volatile release.