Abstract Polystyrene has been copolymerized with 4-vinylbenzyl alcohol, 4-(2-hydroxyethyl)styrene, and 4-(3-hydroxypropyl)styrene and it has been shown that thermal cross-linking of these copolymers is dependent upon the alcohol content. When the alcohol content is low, no thermal cross-linking is observed. When various phosphate esters are present as catalysts with these low alcohol content copolymers, cross-linking is observed at temperatures of about 250°C but not at lower temperatures. Cross-linking enhances the thermal stability of the copolymers. Studies of the thermal stability of the copolymers and their blends with the catalysts have been performed using thermogravimetric analysis and thermogravimetric analysis coupled to Fourier transform infrared spectroscopy. There is little difference in the thermal stability of all three copolymers and their blends with the catalysts.