Thermally stimulated currents (TSC) have been measured in several samples of poly(vinyl chloride) differing in tacticity and molecular weight as a result of polymerizing them at different temperatures. This has allowed us to characterize the relaxation behavior of PVC. No dielectric relaxation can be observed by this experimental technique at temperatures between liquid helium and liquid nitrogen. The β relaxation is observed around 173°K, with similar parameters in all samples studied. Around the glass transition the relaxation times isolated in the α peak follow a compensation law. Molecular weight and tacticity have a strong influence on the temperature of the maximum and the intensity of this relaxation, respectively.