The catalytic behavior of several acidic and alkaline solids was investigated in the heterogeneous dehydration of 2,3-butanediol in the temperature range of 350-800 A degrees C. At low temperatures butanone is the main product for all used catalysts. Its yield decreases with increasing temperatures. The formation of 1,3-butadiene was observed over the whole temperature range. Its maximum formation around 700 A degrees C was explained in term of non-catalytic thermal dehydration. DFT calculations of the dehydration steps were made to explain the results. It was shown, that a hydride shift directs the reaction towards the formation of butanone.