An enantioselective organocatalytic microwave-assisted method for the addition of ethyl trifluoropyruvate to ketones to synthesize highly enantiomerically enriched organofluorine synthons is described. Besides the high yields, diastereo- and enantioselectivities, the most important observation is that the use of microwave irradiation at subzero temperatures proved to be beneficial. The results indicate that subzero temperature microwave chemistry is a potentially intriguing tool for asymmetric synthesis.