Thin films of PVA/PVP blend have been obtained by solution casting method. These films have been subjected to structural (XRD) and optical (FTIR, UV-VIS) studies. The crystallnity of PVA/PVP blends decreases with the increase in concentration of PVP. The FTIR spectra show the blending of PVA and PVP at different concentration. The UV-Vis spectroscopic analysis shows that optical band gap energy of PVA/PVP blends decreases with the increase in concentration of PVP.