Two transition metal complexes as 2, 6-diamino-3, 5-dinitropyridine-1-oxides (ANPyO) with Cr(Ⅲ) and Zn(Ⅱ) were synthesized and characterized by FT-IR spectroscopy and elemental analysis. The effects of Cr(Ⅲ) and Zn(Ⅱ) complexes on the thermal decomposition of RDX, HMX and AP was studied by DSC and TG-DTG. Results show that thermal decomposition of the Cr(Ⅲ) complex only consists of one violent exothermic process with 10.79% residues and the Zn(Ⅱ) complex consists of two consecutive exothermic processes with 12.68% residues. Two complexes have little catalytic effect on the thermal decomposition of RDX and HMX. However, two complexes make the peak temperature of the higher thermal decomposition of AP decrease by 42.40 ℃ and 122.32 ℃, and the exothermic quantity of decomposition reaction increase by 849.5 J·g^-1 and 971.35 J·g^-1, respectively.