In order to evaluate the application value of new azido plasticizers in low-ablation gun propellant formulations, the material optimization and formulation characteristics of gun propellants containing new azido plasticizers were investigated by comparing the properties of plasticizers and calculating the propellant formulations. The results show that 2-nitro-2-azidomethylene-1,3-diazidopropane (NIBTA), 3-azido-2,2-bis(azidomethyl) propyl 2-azidoacetate (ABAMPA) and 1,5-diazido-3-oxopentane (AZDEGDN) are three novel azido plasticizers with excellent overall performance, among which NIBTA is superior to 1,5-diazido-3-nitrazapentane (DIANP) in nitrogen content and oxygen balance, ABAMPA is superior to DIANP in enthalpy of formation, while ABAMPA is superior to DIANP in enthalpy of formation and glass transition temperature. The content of plasticizers, the solvent-nitrocellulose ratio, as well as the content and proportion of high-energy solid additives all have significant effect on the energy characteristics of the propellant formulations containing new azido plasticizers. When the type of plasticizer is the only difference, the force capacity of ABAMPA-containing propellant is the highest, but its detonation temperature is lower than DIANP-containing propellant. In addition, the force capacity of AZDEGDN-containing propellant is obviously higher than NIBTA-containing propellant, whereas its detonation temperature is evidently lower than DIANP-containing propellant. Finally, the propellant formulations containing new azido plasticizers with adequate force capacity and detonation temperature can be designed using nitroguanidine and 2,2-dinitroethene-1,1-diamine as the high-energy solid additives. The detonation temperature of the formulations can be reduced by more than 200 K on the basis of traditional low-ablation propellant formulation. It is concluded that some new azido plasticizers have application prospects in low-ablation propellant formulations, which should be used for further research.