Effect of electron irradiation on the free volume related microstructural and optical properties of chalcone doped Poly(vinyl alcohol) composite films have been studied using FTIR, UVeVisible, XRD and Positron Annihilation techniques. The FTIR spectral study shows that the irradiation induces the crosslinking within the composite. Using UVeVisible absorption spectra the optical energy band gap and activation energies were estimated and the variation of these parameters suggests the existence of defects and molecular ordering within the irradiated composite. XRD diffractograms reveal that the crosslinking enhances the crystallinity of the sample. In this cross-linked polymer composite the fluorescence enhancement has been observed in the fluorescence spectral study. The Positron annihilation result suggests that the irradiation affects the free volume properties and crosslinking hinders the chalcone chromophore molecular rotation. Under this restricted condition the chromophore molec uleslikely to emit enhanced fluorescence and its mobility is directly related to the free volume around it.