The radical reaction of the unsaturated polyester from polycondensation of 1,3-Propanediol (PDO) and itaconic acid (IA) has been successfully performed to create a three-dimensional networking polyester with good thermal stability. Two different crosslinkers of divinyl benzene (DVB) and methylene bisacrylamide (MBA) have been radically reacted on the chain group of polypropylene itaconate (PPIA). The radical reaction of PPIA with DVB and MBA was achieved up to the addition of 30 and 15% (w/w) crosslinkers, respectively. PPIA reacted with aromatic-content of DVB showed higher thermal stability compared to acrylic derivate crosslinker of MBA. The increase in the crosslinking density on the propylene itaconate (PIA) slightly enhanced the thermal stability of the polyester. This study concludes that the limitation of the use of PDO as a raw material as a source for polyester could be avoided by a strategy of condensation with unsaturated diacids (as IAs) and radical reaction with crosslinking agents. (C) 2016 Elsevier B.V. All rights reserved.