6, 6, 6-Tri-and 6, 6-difluoromevalonate were synthesized by new method starting from the corresponding β-alkoxyvinyl polyfluoromethyl ketones. Enantiomers of fluoromevalonates were obtained by column chromatography separation of diastereomeric (S)-(−)-1- phenylethylamides of fluoromevalonates with the following hydrolysis. Racemic 6, 6, 6-tri- and 6, 6-difluoromevaldates were also prepared.