Poly(vinyl alcohol) nanowebs were prepared by electrospoinning technique. The electrospinning technique produced nanometer scale of polymer fibres. This technique used the electrostatic force draw the polymer solution from the needle tip and deposited on substrate to from nanowebs. The PVA nanowebs were prepared with various surfactant types (anionic, cationic and nonionic surfactant). The cetyltrimethylammonium bromide, polyethylene glycol sorbitanmonolaurate, polyoxyethylenesorbitanmonolaurate, sodium lauryl sulfate were employed as surfactants. The morphology of PVA nanowebs were investigated using scanning electron microscope (SEM). The SEM micrograph shows that PVA nanowebs with all surfactants were successfully prepared with no beat. Thermal properties were measured by using differential scanning calorimetry (DSC). The results show that the %crystalline of PVA with SLS surfactant was slightly decreased. The mechanical property of nanowebs were measured using universal testing machine. The structure of nanowebs were analyzed by x-ray diffraction technique.