Ionic liquids such as 1,3-dialkylimidazolium bromides make excellent solvents for synthesis of alpha-aminophosphonates from aldehydes, amines, and phosphites. The ionic liquids are successfully regenerated and reused. (C) 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:625-629, 2011; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20724