The palladium-catalyzed desulfitation Heck coupling reaction of sodium arylsulfinates with acrylates in weak polar solvent using silver hexafluoroantimonate as additive to synthesize cinnamates was realized. The structures of products were characterized by 1HNMR, 13CNMR and HRMS. The results showed that silver hexafluoroantimonate activated the palladium catalyst and promoted the desulfitation Heck coupling reaction between sodium arylsulfinates and acrylates in toluene. The yields of the products in air atmosphere were higher than those in oxygen or nitrogen atmosphere. The analysis of reaction mechanism revealed that oxygen was not conducive to the triphenylphosphine ligand-involved regeneration process of the palladium catalyst, but was beneficial to the regeneration of copper acetate oxidant.