The feasibility of Fe(Ⅲ) and Co(Ⅲ) energetic complexes of 2, 6-diamino-3, 5-dinitropyridine-1-oxide (ANPyO) as combustion catalysts was tested by closed bomb test and target lines experiment. Results show that the two complexes have obvious catalytic effects on the combustion of double-base gun propellants and triple-base gun propellants by increasing of the burning rate and decreasing of the pressure exponent by 2.97%-11.36%. The Fe(Ⅲ) complex has significant catalytic effects on the combustion of double-base propellants with the burning rate increasing by more than 20% in the pressure range of 10-20 MPa and the pressure index decresing by 25.30%-45.78% at 10, 14, 18, 20 MPa, respectively. While, the catalytic effect of Co(Ⅲ) complex on double-base propellant is not obvious.