Degradation of a model polymer mixture (PVC/PS/PE) and a waste polymer mixture in the presence of HCl fixators (Red Mud, precipitated CaCO3 and dolamite) was studied using thermal gravimetric analysis (TGA) and a cycled-spheres-reactor. The experiments in cycled-spheres reactor model were performed by stepwise pyrolysis. Liquid products and HCl from each step were collected separately. For the model polymer mixture, the precipitated CaCO3 showed the best effect on the fixation of evolved HCl and the reduction of chlorine content in the liquid products whereas RM yielded the best result for the waste polymer mixture. In addition, using HCl fixator also affected the degradation of both types of polymer mixture, leading to the formation of more gaseous and less residue.