The thermal oxidative aging of a crosslinked hydroxy-terminated polybutadiene (HTPB)/isophorone diisocyanate (IPDI) based polyurethane rubber, used as a polymeric binder in solid propellant grain, was investigated at temperatures from 25 to 125 °C. The changes in tensile elongation, polymer network properties and chain dynamics, mechanical hardening and density were determined with a range of techniques including modulus profiling, solvent swelling, NMR relaxation and O2 permeability measurements. We critically evaluated the Arrhenius methodology that is commonly used with a linear extrapolation of high temperature aging data using extensive data superposition and highly sensitive oxygen consumption experiments. The effects of other constituents in the propellant formulation on aging were also investigated. We conclude that crosslinking is the dominant process at higher temperatures and that the degradation involves only limited hardening in the bulk of the material. Significant curvature in the Arrhenius diagram of the oxidation rates was observed. This is similar to results for other rubber materials.