Poly(vinyl chloride) has been modified by chlorine displacement reaction with 2-anthrol and anthraquinone-2-ol. The condensates (PVC-ACOL and PVC-AQOL) are insoluble in all solvents common to PVC and have been characterized by elemental and IR spectra analysis. The initial decomposition temperature of these condensates follow the trend: PVC-AQOL (250°C) > PVC-ACOL (200°C) > PVC(190°C) and the overall thermal stabilities beyond 60% decomposition follows the same trend. Permittivity and dielectric loss of these condensates sharply fall with increasing applied frequency (10–1.3 ×107 Hz) to a limiting constant value. In contrast, for unmodified PVC these values are low and remain independent of frequency in the same range. Sulfonation of these PVC condensates affords a weak acid resin with COOH and OH ionogenic groups, but no strong sulfonic acid groups due presumably to oxidative degradation of the PVC matrix.