α,β-unsaturated esters were often synthesized from aldehydes and esters in the presence of strong organic base that was very sensitive to air and moisture via aldol reaction.Trioxane was very useful C1 resource,however,the decomposition of it was always the challenging problem that facing researchers.Herein,a novel synthetic methodology for α,β-unsaturated ester preparation from trioxane and ester with mild catalysis of generated ammonium trifluoromethanesulfonate ionic liquid.The enolization of ester as well as the decomposition of trioxane could proceed easily in the presence of boryl trifluoromethanesulfonate and amine at 20--25 ℃.Then the enolate and decomposed formaldehyde occurs aldol reaction to form α,β-unsaturated ester.With this strategy,the yield and selectivity of product from various substrates including aliphatic esters,lactones and thioester could reach up to 85.2％ and 90.1％.