The present work developed a novel process to separate polyvinyl chloride (PVC) and Cu from electric cables by the combination of de-plasticizer from PVC and ball milling processes. The covering PVC commonly includes plasticizer to obtain flexibility, and de-plasticized PVC cables were improved to be brittle, which can be easily crushed by physical impact. In this work, plasticizers in the electric cables, which of sizes were 0.3 and 1.25 mm², were extracted by soxhlet and dipping methods using diethyl ether, then the extracted samples were crushed by using a ball-mill. The influences of extraction method and extraction rate on the ball milling separation were investigated. The highest separation rates of 100% and copper separation accuracy of 99.6% were achieved with de-plasticized 0.3mm² cable sample, while those of 1.25mm² cable sample were little lower as 83% and 98.3%.