Polyethylene terephthalate (PET) is one of the most widely used macromolecule materials, but the treatment of waste PET has been a great challenge to environment safety. In this article, we report for the first time an effective method to produce gaseous products containing acetylene, ethylene and carbon monoxide from PET particles using a rotating direct current arc plasma reactor. Thermodynamic simulation was performed, and the effect of input power, PET feed rate and working gas flow rate on PET pyrolysis was experimentally investigated. An almost complete carbon conversion could be achieved by this method with a product gas containing 42% acetylene, 53% carbon monoxide and 4% ethylene, while the specific energy consumption of product gas was below 20 kWh/kg. These results show that rotating arc plasma is a promising method of improving the conversion of waste PET to valuable hydrocarbons and syngas.