Abstract: Pyrolysis is an effective way for clean and efficient use of coal, as well as an important way for the efficient conversion of waste plastics. Polyvinyl chloride (PVC) and Pingshuo (PS) coal were used in this research object. A two-step treatment scheme was proposed for chlorine-containing plastics that are difficult to be treated harmlessly. The PVC was preheated to remove most of the chlorine, and then the pretreated PVC residue (DPVC) and coal were co-pyrolyzed. GC, simulated distillation, GC-MS, elemental analysis, FT-IR and Raman spectroscopy were used to analyze and characterize the composition and properties of pyrolysis gas, tar and char. The results showed that the co-pyrolysis process of DPVC and PS coal has a synergistic effect, and the co-pyrolysis has an obvious positive synergistic effect on the formation of char and tar. The experimental value of tar yield is higher than theoretical calculation and the maximum increasing value is 3.35%. There is a negative synergistic effect on the formation of pyrolysis water and gas, in which CH₄ has the largest decrease in yield, meaning the strongest negative synergy. Co-pyrolysis increases the content of light tar, significantly increases the content of naphthalenes, and reduces the asphalt. When the DPVC addition was 10%, the content of light tar increases by 5 percentage points over the theoretical calculation value. In addition, the co-pyrolysis char surface is smoother, the structure becomes more orderly, and the graphitization degree increases.