Miscibility, thermal, mechanical, gas permeation, morphological and surface properties of poly(vinyl chloride) (PVC) blends containing 1-10% triblock polycaprolactone-poly(dimethylsiloxane)-polycaprolactone (PCL-PDMS-PCL) copolymer were investigated by using several techniques. Fourier transform infra-red analysis of blends reveal the existence of specific interactions via hydrogen bonding between the alpha-hydrogen of PVC and the carbonyl group of PCL in the triblock copolymer. This PCL-PDMS-PCL/PVC blend system exhibited a single glass transition according to differential scanning calorimetry and dynamic mechanical thermal analysis results. Stress-strain results showed that PCL-PDMS-PCL triblock copolymer is a very effective plasticizer for PVC. Gas permeability of the blends increased with the copolymer content. Morphological and surface properties of the blend system were examined by scanning electron microscopy and contact angle measurements.