An energetic analysis of the thermal decomposition of solid urea and urea solutions is presented, and the results are discussed in view of urea selective catalytic reduction (SCR) for automotive DeNOx systems. Various types of decomposition reactors are possible which differ in their effectiveness to produce ammonia from urea. For reasons of simplicity, the decomposition is usually performed by atomizing urea solutions directly into the hot exhaust. However, this technique suffers from short residence times, leading to incomplete decomposition into ammonia and isocyanic acid and causing a significant performance loss of the SCR catalyst. The thermal decomposition out of the main exhaust stream allows much increased residence times for the process of urea decomposition. A reactor utilizing a partial stream of the exhaust seems particularly promising, especially if such a reactor includes a hydrolyzing catalyst, leading to ammonia practically free from isocyanic acid.