The constant-volume combustion energy Δ_cU (4HDNPPb,s,298.15 K) of lead salt of 4-hydroxy-3,5-dinitropyridine (4HDNPPb) was determined as (－7385.82±3.14) J·g^－1 at 298.15 K by a precise rotating bomb calorimeter. The standard molar enthalpy of combustion Δ_cH^θ_m (4HDNPPb,s,298.15 K) and standard molar enthalpy of formation Δ_fH^θ_m (4HDNPPb,s,298.15 K) of 4HDNPPb were calculated to be (－4499.63±1.92) kJ·mol^－1 and (－796.65±2.32) kJ·mol－1,respectively. Moreover,the catalysis of composite catalyst system,4HDNPPb/energetic copper salt mixture or 4HDNPPb/non-energetic copper salt mixture on the combustion of RDX-CMDB propellant was investigated. The results show that composite catalyst, 2.5%/0.5%-ω(4HDNPPb)/ω(2HDNPCu) mixture or 2.5%/0.5%-ω(4HDNPPb)/ω(-Cu,copper phthalate) mixture,has higher catalytic efficiency in catalyzing RDX-CMDB propellant combustion and enables the pressure exponent of the propellant to be less than 0.3。