In in situ consolidation of thermoplastic composites by laser-assisted automated fibre placement (AFP), high laser irradiation temperature can improve the fluidity of the resin matrix, which usually enhances the performances of composites. However, it leads to a tendency for thermal degradation as the resin matrix of the composites is exposed to high temperatures for a long time. The thermal degradation behaviours of continuous carbon fibre (CF)-reinforced polyphenylene sulfide (PPS) composites during in situ consolidation by laser-assisted AFP were studied. A thermogravimetric analysis shows that the thermal degradation of CF/PPS composites is quite complex, with multi-step reactions. The thermal degradation of the composites was further analysed via kinetic methods. A thermal degradation kinetic model of the resin matrix was obtained and verified. According to the kinetic model, the thermal degradation of the composites under different placement conditions was predicted. The results were confirmed by Fourier-transform infrared spectroscopy and scanning electron microscopy. With the combination of the kinetic model, AFP in situ consolidation, and characterisation techniques, processing parameters such as laser irradiation temperature and placement speed can be adjusted and optimised.