Novel nanocomposites of PEO/PVDF loaded by different contents of SWCNTs were prepared. From UV-Vis spectra, the estimated values of absorption edge, absorption coefficient, energy of tail and extinction coefficient were calculated. The exponential decay tail at low energy is due to the presence of localized states in the energy band gap. The shift of Raman spectra indicates the possibility of SWCNTs to be attached with OH group in the side chain of polymer molecules. The X-ray measurements indicate that the addition of SWCNTs is a rich amorphous region in polymeric matrices and complete complexation between PEO/PVDF blend and SWCNTs. The SEM images show smooth surface of PEO/PVDF and they become rough with single rod with a good distribution within surface region in polymeric matrices after loading SWCNTs. TEM images showed that SWCNTs were dispersed well in polymeric matrices. The broken ends of nanotubes were showing that the SWCNTs were broken apart rather than from at the fracture surface. The films show some defects like rags on the tube walls. There are some black regions in TEM images attributed to amorphous nature carbon. The prepared nanocomposites are very useful in technical application.