The effect of the burning rate catalysts Fe₂O₃, CuO, Cr₂Cu₂O₅, PbCO₃, C₆H₅O₇Pb, lead salt 3-nitro-1, 2, 4-triazole-5one (NP), and carbon black(CB) on the thermal decomposition properties of GAP-based ETPE were investigated by TG and DSC. The results show that several burning rate catalysts have a great influence on the thermal decomosition of of azide groups in the GAP-based ETPE, in which, CuO and Cr₂Cu₂O₅ make the thermal decomposition peak temperature of azide groups in GAP-based ETPE decrease by 21.9 ℃ and 13.6 ℃, respectively, but Fe₂O₃, PbCO₃, C₆H₅O₇Pb, NP and CB make the thermal decomposition peak temperature of azide groups in GAP-based ETPE increase by 1.7, 2.6, 1.6, 1.0 ℃ and 1.1 ℃, respectively. CuO, Cr₂Cu₂O₅, C₆H₅O₇Pb and CB make the apparent decomposition heat of azide groups in GAP-based ETPE increase by 75.5, 84, 43.4 J·g^-1 and 103.1 J·g^-1 respectively. However, Fe₂O₃, PbCO₃ and NP make the apparent decomposition heat of azide groups in GAP-based ETPE decrease by 137.9, 58.8 J·g^-1 and 47.3 J·g^-1.respectively. After the comprehensive comparison, considering that CuO and Cr₂Cu₂O₅ make the thermal decomposition peak temperature of azide groups in GAP-based ETPE decrease and the apparent decomposition heat increase, they are ideal catalysts of catalyzing the thermal decomposition of the GAP-based ETPE.