Ethyl acrylate and acrylonitrile fail to undergo efficient Baylis-Hillman reaction with fluoral, but provide good yields of products with pentafluorobenzaldehyde. Alternately, unsubstituted and beta-substituted [alpha- (ethoxycarbonyl)vinyl]aluminum react with perfluoroalkyl and -aryl aldehydes and ketones to provide the alpha-hydroxyalkenylated fluoroorganic compounds in good to excellent yields. (C) 1998 Elsevier Science Ltd. All rights reserved.