This study inspected the thermal decomposition kinetics of core-shell structured wood-plastic composite material with white mud loading in the shell. The thermal decomposition was studied via thermogravimetric analysis under nitrogen atmosphere. Experiments were performed at different heating rates of 5, 10, 20, 30, and 40 °C/min from ambient temperature to 700 °C. Multivariate linear regression analysis was applied to estimate the activation energy with the Flynn–Wall–Ozawa method, and the thermal aging life equations of composites were obtained as described in ASTM E1877 (2000). The results showed that the combustion characteristic parameters (T5%, Tp1, Tp2, and Tp3) increased at first and then decreased with increased white mud concentration. Accordingly, the average apparent activation energy (Ea) values of thermal decomposition with conversion rates ranging between 20% and 80% were 222 kJ/mol for high-density polyethylene (HDPE) shell layer and the average values of 201, 226, 201, 207, and 223 kJ/mol were achieved with white mud loading of 5, 10, 15, 20, and 25% in the shell layer, respectively. There were no remarkable dependencies among them. The service life tf (min) and the service temperature T (K) of the core-shell structured wood-plastic composites were experimentally determined.