While the use of plastics continues to increase in our daily lives in a growing range products, these materials are very persistent in the environment. The blending of aliphatic polyesters with other thermoplastic polymers is a profitable way of producing materials with changed physical properties and biodegradability, which can facilitate microbial adhesion to the polymer matrix and help to reduce (post-consumer) degradation time of these materials in landfills. This study was an investigation of the biodegradation of films of blends of poly(vinyl chloride (PVC) and poly(ε-caprolactone) (PCL) by soil microorganisms and leachate, by means of respirometry, infrared absorption spectroscopy (FTIR), differential calorimetry scanning (DSC), scanning electron microscopy (SEM), contact angle and weight loss. The results showed that in the soil, the films suffered oxidative biodegradation. The PCL promoted degradation of the PVC in the film of PVC/PCL and the PVC inhibited the rapid degradation of the PCL.