One-step synthesis of acrylates from acetates and trioxane via aldol reaction at 623 K-653 K was reported. But proceeding this process at room temperature is still a challenge due to ester activation and trioxane decomposition. Herein, series of acrylates were firstly achieved, with the one-step and in-situ catalytic strategy, from acetates (or propionates) and trioxane at 293 K. Selectivity of product reaches up to 94.4% with a 80.8% yield. H-1 NMR confirmed the soft enolization of ester, the decomposition of trioxane was catalyzed by TMSOTf, and the generated ionic liquid has catalytic performance on aldol condensation step. (C) 2017 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.