This work presents direct measurements of the temperature distribution during impact loading of cyclo-tetra-methylene-tetra-nitramine–hydroxyl terminated polybutadiene material at the mesoscale with sub-microsecond/micrometer resolution. The focus is on analyzing the effect of impact loading on microstructure-dependent material behavior. The temperature distribution is shown to be strongly correlated to the local material microstructure with the interface and particle shape playing a key role. © 2019, The Minerals, Metals & Materials Society.