GigaHertz (GHz) thermoreflectance technique is developed to measure the transient temperature of metal and semiconductor materials located behind an opaque surface. The principle is based on the synchronous detection, using a commercial THz pyrometer, of a modulated millimeter wave (at 110 GHz) reflected by the sample hidden behind a shield layer. Measurements were performed on aluminum, copper, and silicon bulks hidden by a 5 cm thick Teflon plate. We report the first measurement of the thermoreflectance coefficient which exhibits a value 100 times higher at 2.8 mm radiation than those measured at visible wavelengths for both metallic and semiconductor materials. This giant thermoreflectance coefficient κ, close to 10−3 K−1 versus 10−5 K−1 for the visible domain, is very promising for future thermoreflectance applications.