Films of polyvinyl alcohol (PVA), Methacrylic Acid - Ethyl Acrylate (MAA:EA) copolymer and their blends PVA:MAA:EA of composition 80:20, 60:40, 50:50, 40:60, 20:80 (wt %) were prepared by using the solution cast technique. The prepared films were investigated by structural, optical and thermal studies. X-ray diffraction (XRD) scans revealed the semicrystalline nature of the blends for lower concentrations of PVA up to 60 wt % and the amorphous nature for higher ones. Fourier transform infra-red spectroscopy (FTIR) of blend samples indicates that there is a compatibility between PVA and MAA:EA copolymers through the formation of hydrogen-bonding between their polar groups. SEM image of polymer blend suggested the presence structural reorganization of polymer chains. UV-Visible spectral analysis revealed that the intensity of the shoulder around 271 nm decreases with increasing MAA:EA content. In DSC analysis, a single glass transition temperature for each blend was observed, which supports the existence of compatibility of such systems. From the observed results, 50:50 (wt %) PVA/MAA:EA is found to be the optimum blending ratio.