2，4，8，10-Tetranitro-benzopyrido-1，3a，6，6a-tetraazapentalene （NBTTP） was synthesized from 1H-benzotriazole and 2-chloro-3-nitropyridine via displacement， cyclization and nitration.The structure of NBTTP was characterized by FTIR and NMR. In addition， the reaction condition of cyclization was optimized. Its thermalbehavior was analyzed by TG-DTG， while its thermal decomposition behavior， kinetic parameters and thermodynamic parameters were obtained by DSC. The results shows that the highest yield was up to 83.44%， when the molar ratio of triethylphosphite and the BTP was 3∶1. NBTTP presents a main single exothermal event with initial at around 388.79 ℃ and maximum at around 406.23 ℃. Its non-isothermal kinetics equations of thermal decomposition may be described as dα/dt=（6.36×10¹⁴/β）（1-α）exp［-2.34×10⁵/（RT）］. The entropy （ΔS^≠）， enthalpy （ΔH^≠）， free energy （ΔG^≠） and self-accelerating decomposition temperature （T_SADT） were 23.60 J·mol^-1·K^-1， 228.97 kJ·mol^-1， 213.46 kJ·mol^-1 and 655.11 K， respectively.