There is a large amount of shells generated as a waste product from industrial processes. Therefore, the high-value utilization of shells is a hotspot of current research. The thermal characteristics and kinetics of waste Camellia shells (WCOSs) were analyzed by thermogravimetry with gas chromatography-mass spectrometry (TG-GC/MS). The thermal behavior of WCOSs was studied at 10, 20, 40, and 60 °C/min, and the distributed activation energy model (DAEM) was used to research the kinetics and activation energies. The activation energies of WCOSs based on the DAEM ranged from 68.64 to 244.49 kJ/mol, corresponding to the conversion rate from 0.10 to 0.90. The correlation coefficient () shows the best fit, and it ranged from 0.921 to 0.994. Pyrolysis products at four key temperature points (228, 296, 492, and 698 °C) were studied via GC/MS. Many compounds were detected at the different temperatures. With the increase of temperature, furans, benzene, and long-chain alkanes were produced successively. This data will help to expand the utilization of WCOSs.