Poly(ethylene terephthalate) waste materials were depolymerized by ethylene glycol (EG), diethylene glycol (DEG), and propylene glycol (PG) in the presence of a novel catalytic system: titanium (IV)-phosphate. The new catalyst was synthesized through a reaction of TiCl4 with triethyl phosphate (C2H5O)(3)P(O). It was found that the depolymerization of poly(ethylene terephthalate) fiber proceeds faster in the presence of titanium (IV)-phosphate compared with compounds traditionally used in this process like Zn(OOCCH3)(2). The oligomer distribution in the glycolysis products was studied by size-exclusion chromatography. (C) 2003 Wiley Periodicals, Inc.