Emissions evolved from the pyrolysis and combustion of poly(vinyl chloride) were studied at four different temperatures (500, 700, 850 and 1000 8C) in a horizontal laboratory tubular quartz reactor in order to analyse the influence of both temperature and reaction atmosphere on the final products from thermal and oxidative reactions. It was observed that the CO 2 /CO ratio increased with temperature. Methane was the only light hydrocarbon whose yield increased with temperature up to 1000 8C. Benzene was rather stable at high temperatures, but in general, combustion at temperatures above 500 8C was enough to destroy light hydrocarbons. Semivolatile hydrocarbons were collected in XAD-2 resin and more than 160 compounds were detected. Trends on polyaromatic hydrocarbon (PAH) yields showed that most had a maximum at 850 8C in pyrolysis, but naphthalene at 700 8C. Formation of chlorinated aromatics was detected. A detailed analysis of all isomers of chlorobenzenes and chlorophenols was performed. Both of them reached higher total yields in combustion runs, the first ones having a maximum at 700 8C and the latter at 500 8C. Pyrolysis and combustion runs at 850 8C were conducted to study the formation of polychlorodibenzo-p-dioxins (PCDDs) and polychlorodibenzofurans (PCDFs). There was more than 20-fold increase in total yields from pyrolysis to combustion, and PCDF yields represented in each case about 10 times PCDD yields. #