Instantaneous temperature measurements at the interface between a solid wall and a thin, unsteady liquid film are performed using thermoreflectance, a nonintrusive optical technique with high temporal resolution. A laser beam is directed at a wall–liquid interface, and the intensity of the light reflected at that interface is measured by a photodiode. The intensity of the reflected light varies with the index of refraction of the liquid at the wall. The index of refraction is a function of temperature, which enables the instantaneous measurement of the wall temperature. In the presence of thin liquid films, reflections from the liquid–vapor interface at the free surface of the film generate noise in the measurements. We demonstrate that orienting the laser beam at a large incident angle, close to total internal reflection, minimizes noise from the liquid–vapor interface while increasing the sensitivity of the measurement. The thermoreflectance technique is validated in an unsteady two-phase annular flow. Measurements of temperature fluctuations less than 1 K in amplitude are achieved, with an uncertainty of 0.1 K.