The accumulation of plastics in the environment is raising great concerns with respect to long-term environmental, economic and waste management problems. The aim of the present research was to investigate the biodegradability of starch blended polyvinyl chloride films in soil burial and controlled laboratory experiments using selective fungal isolates. Clear surface aberrations as color change and minor disintegration in polyvinyl chloride films were observed after 90 days and later confirmed through scanning electron microscopy. The fungal strains showing prominent growth and adherence on plastic films were isolated. One of the strains showing maximum activity was selected and identified as Phanerochaete chrysosporium PV1 by rDNA sequencing. Fourier transform infrared spectroscopy and nuclear magnetic resonance analyses indicated considerable structural changes and transformation in films in terms of appearance of new peaks at 3,077 cm−1 (corresponding to alkenes) and decrease in intensity of peaks at 2,911 cm−1 (C–H stretching). It was supported with a significant decrease in the molecular weight of polymer film from 80,275 to 78,866 Da (treated) through Gel permeation chromatography in shake flask experiment. Moreover, the biodegradation of starch blended polyvinyl chloride films was confirmed through release of higher CO2 (7.85 g/l) compared to control (2.32 g/l) in respirometric method. So fungal strain P. chrysosporium PV1 has great potential for use in bioremediation of plastic waste.