The surface urban heat island (SUHI) effect is defined as the increased surface temperatures in urban areas in contrast to cooler surrounding rural areas. In this article, the evaluation of the SUHI effect in the city of Madrid (Spain) from thermal infrared (TIR) remote-sensing data is presented. The data were obtained from the framework of the Dual-use European Security IR Experiment (DESIREX) campaign that was carried out during June and July 2008 in Madrid. The campaign combined the collection of airborne hyperspectral and in situ measurements. Thirty spectral and spatial high-resolution images were acquired with the Airborne Hyperspectral Scanner (AHS) sensor in a 11, 21, and 4 h UTC scheme. The imagery was used to retrieve the SUHI effect by applying the temperature and emissivity separation (TES) algorithm. The results show a nocturnal SUHI effect with a highest value of 5 K. This maximum value agrees within 1 K with the highest value of the urban heat island (UHI) observed using air temperature data (AT). During the daytime, this situation is reversed and the city becomes a negative heat island.