A solventless benzoin condensation was performed with several imidazolium-based ionic liquids as catalysts under microwave irradiation. The process enables the formation of alpha-hydroxy-alpha-phenylacetophenone with good yield (up to 97%) and purity in a very short time. Moreover, the work-up only requires the use of water, giving a green touch to the overall process. (c) 2006 Elsevier B.V. All rights reserved.