In the present study, the drop cast films of polyvinyl alcohol (PVA), polyethylene glycol (PEG) and optimized PVA:PEG (50:50) polyblend were studied. The pure polymer and polyblends samples were characterised by using Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR) and Optical Absorption Spectroscopic Techniques. Changes in the morphology of optimized PVA:PEG polyblend has been observed in SEM photographs. FTIR results have been observed to form H-bond between PVA and PEG which confirms the plasticizing effect of PEG on PVA. The absorption maxima is observed at 325 nm and 300 nm for the pure PEG and PVA samples, while it is found to shift to 320 nm for the polyblends. The shift in peak related to absorption edge may attribute to the change in polymeric chain mobility as well as crystallization behaviour during the blending process. The value of indirect optical gap is found to be 1.75 eV, which very less as compared to the pure components. An increase in the value of B⁻¹ has been observed indicating an enhancement of disorder with the formation of polyblends. These results are very important for realizing their applications as optical components.