Abstract: The present invention relates to a novel catalyst composition and a novel process for synthesizing methyl acrylate from methyl formate and acetylene, in which methyl formate reacts with acetylene in the presence of a main catalyst comprising one or more compounds selected from RuCl.sub.3, Ni(CH.sub.3 COO).sub.2, NiBr.sub.2, NiI.sub.2, NiSO.sub.4, Ni(NO.sub.3).sub.2, PdCl.sub.2, CoCl.sub.2, Rh.sub.3 (CO).sub.12 and RhCl.sub.3, and the catalyst promoter comprising one or more compounds selected from CuSO.sub.4, NaI, KI and CH.sub.3 I, at a temperature of 120.about.240.degree. C., and under reaction pressure of 1.0.about.10.0 MPa, a molar ratio of methyl formate to acetylene ranges form 0.1:1 to 20:1. The yield of methyl acrylate may reach to 63%.