The current research focuses on the usage of modified chitosan as facilitator to influence the stereo-complexation of high molecular weight poly(D-lactic acid)/poly(L-lactic acid) (PDLA/PLLA) blend. Solution cast films of PDLA/PLLA blend with varying amount of modified chitosan (MCH) yields the formation of stereocomplex crystallites and diminishes the content of homocrystallites in the PDLA/PLLA blend confirmed by several techniques such as DSC, FTIR and XRD. The melting point is found to be more than 205 degrees C with the heat of fusion as 50 J g(-1). However, the degree of crystallinity of the stereocomplex crystallites, is observed to be more than 56% with MCH loading of 3%. The prepared biocomposite films have been analyzed for oxygen permeability in order to explore their probable application in the packaging industry. Improved stereocomplexation reduces the oxygen permeability and the reduction has been found to be 56% for 3 wt% MCH loading w.r.t sPLA and a reduction of 84% was observed when compared to pristine PLA. Formation of the stereocomplex crystallites into the matrix also enhances the hydrophobicity of the prepared film. Further, the MTT assay is conducted using BHK-21 cells which confirms the adhesion and proliferation of cells on the developed films indicating the biocompatible nature of the films. (C) 2017 Published by Elsevier Ltd.