The catalytic effects of CuAl layered double hydroxide (CuAl-LDH) on dechlorination and carbonization of polyvinyl chloride (PVC) during pyrolysis were investigated. The thermal degradation and combustion behaviors were researched via thermogravimetric analysis (TGA) and cone calorimetry (CONE). The released gases were evaluated in detail by thermogravimetric analysis coupled with Fourier transform infrared spectrometry (TGA-FTIR). Subsequently, elemental analysis and scanning electron microscopy-energy dispersive spectrometry (SEM-EDS) were employed to fully characterize the solid residues. The results of TGA and CONE showed that the addition of CuAl-LDH brought about the PVC degradation earlier and the char residues increase significantly. Moreover, the results of TGA-FTIR, elemental analysis, SEM-EDS, and Raman analysis revealed that the existence of CuAl-LDH accelerated the dehydrochlorination and promoted the char formation of PVC. CuAl-LDH maybe a potential catalyst applied to treat PVC waste into carbon materials to realize material and chemical recycling, which possess tremendous environmental and economic benefits.