The structure, development, morphology, and dielectric relaxation have been investigated in poly(vinyl chloride)–thermoplastic elastomer (copolyester–ether) blends having different compositions. The changes in the intensities of dielectric relaxation peaks for the β and γ processes with respect to blend composition have been found to be associated with corresponding changes in crystalline structure and morphology of the elastomeric component. The critical composition for observing such modification of properties is about 50% of poly(vinyl chloride) above which the blend becomes almost amorphous. © 1994 John Wiley & Sons, Inc.