Nanofibers are a new class of material with unique features and a wide scope of uses. This research article studies the preparation of a novel polymer nanofiber composite from polyvinyl alcohol (PVA) (10%) blended with carboxymethyl cellulose (CMC) (2.5%) with different doses of Poly Ethylene Glycol (PEG) (0.25, 0.5, 0.75 g). Four different samples of PEG0, PEG1, PEG2 and PEG3 were prepared (6.25,7.5, 8.75 and 10 total % (w/v) respectively and The morphology and the average diameter of the electro spun fibers were observed using Scanning-electron microscopy (SEM). The SEM analysis was used also to help in optimizing the PEG concentration and the electrospinning condition (needle-to-collector distance, voltage, and flow rate), that can be used for the preparation of nanofiber membrane composed of PVA/CMC/PEG. The results showed that the nanofiber morphology and diameters of the nanofibers (PEG1, PEG2 and PEG3) were enhanced and the beads disappeared with increasing the PEG concentration and the optimum values for the electrospinning parameters to obtain PEG3 nanofibers with less average diameter are flow rate of 1ml/h, Voltage of 25 kV and Needle-to-collector distance of 25 cm with average diameter of electro spun nanofibers 362 nm. Also the thermal stability of the PVA/CMC/PEG (PEG3) nanofiber membrane was investigated by TGA. The results explained that the sample lost about 7 % at 115 ̊C in the first stage, and lost 93 % after reaching 550 ̊C as second stage of polymer degradation. The water contact angle (WCA) for PEG3 was measured to assess the water absorption and swelling properties of the membrane and the results showed the WCA was 45.35. This value was evidence that the membrane had hydrophilic properties. Treatment with cross linking is necessary if it will use in waste water applications.