In this study, the structure characteristics and combustibility of anthracite (LC), waste plastics (PVC), and their blends were investigated using laser particle size analyzer, Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, scanning electron microscopy, and thermogravimetric analysis. Results show that basic structural features of carbon in PVC and LC are quite different; LC had different carbon rings that constituted carbon layers and some aliphatic chains in the gap of carbon layers, while PVC is composed mainly by long chains. PVC presents high reactivity mainly due to its more disordered crystalline structure. Through kinetic analysis, it is found that the combustion processes of PVC, coal, and their blends have a very consistent fit with the double parallel reactions random pore model (DPRM). The combustion of the blends is divided into two stages, and for each stage, the activation energy first decreases and then increases with the increase of the PVC. When the proportion of PVC is 80%, each stage of the activation energy achieves the smallest value (first stage 43.9 kJ/mol, second stage 31.4 kJ/mol).