A novel method based on pyrolysis-capillary gas chromatography-mass spectrometry (CGC-MS) was developed for the quantitative analysis of polyvinylchloride (PVC) in solid environmental samples like sludge and dust. The samples are extracted and the extract is fractionated by solid-phase extraction (SPE). Possibly interfering biological and frequently occuring synthetic polymers are removed by this clean-up. The final extract is analyzed by pyrolysis-CGC-MS. Selective detection of PVC is performed by using specific markers in the pyrogram. Quantitation is done on naphthalene. Good linearity was obtained in a range from 0.5 to 100 microg applied to the pyrolyser. The limit of quantitation (LOQ) in sludge and dust samples is 10 mg/kg dry mass. A correlation between PVC and phthalates was made for sewage sludge samples.