Reducing loss in microwave dielectrics is critical to improving performance in wireless communications systems. Grain boundaries in polycrystalline microwave dielectric ceramics have long been suspected of increasing dielectric loss. They are often cited as the main contributor to the observed difference in dielectric losses between single crystals and polycrystalline ceramics. The exact configuration of grain boundaries is problematic to quantify in practice and their influence on the dielectric loss difficult to distinguish from other defects such as porosity, oxygen vacancies, impurities, and dislocations. Here we measure the sensitivity of a single grain boundary in a magnesium oxide bi‐crystal to the polarization of an applied microwave field as a function of temperature.