Abstract-This paper dealt with the synthesis and characterization of the polymeric product by the reaction of the water-soluble poly (vinyl alcohol)[PVA] nonwoven fabrics and the phosphoryl chloride (POCl3), which has been applied to prepare water-proofing materials or intermediates for increasing water-proofing or fire-proofing ability of commercially available water-soluble PVA support layer. POCl3 was reacted with PVA nonwoven fabrics under non-aqueous condition, and their reactivity, and chemical structure were checked and discussed. PVA was reacted with POCl3 under the reaction condition of 1:1, or 1:2 mole ratios at 70, 80 and 90℃, and the reaction products were further hydrolyzed. The structure of the resulting products from water soluble PVA nonwoven fabrics reacted with POCl3 were identified by FT-IR or X-ray fluorescence spectrophotometer, and they indicated the PVA polymer chains to have phosphorous and chlorine moieties.