AbstractHydroxyl terminated polybutadiene (HTPB) is widely used as a propellant binder. A plasticizer is usually added to improve the processing properties, the mechanical properties, and the burning characteristics of the propellant. Glycerin was found to be an effective additive to improve these properties. The glycerin/HTPB blend was hard enough to act as a binder for the composite propellant when the glycerin/HTPB mole ratio was less than 10. Only a small quantity of glycerin was incorporated into the network structure of the cured HTPB. Most of the added glycerin physically entered the voids in the network of the cured HTPB. Addition of a small quantity of glycerin (mole ratio less than 0.1) significantly altered the network density and the viscoelastic properties of the blends. The properties were only slightly dependent on the amount of the added glycerin in the mole ratio range of 0.1–10. The dangling ends were formed in the HTPB network by the addition of glycerin and the network structure was loosened, thereby enhancing the mobility of the chain segment. The viscoelastic properties of the blends followed the time‐temperature superposition principle, and the properties were estimated accurately by the Williams‐Landel‐Ferry approach. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011