Vinylphosphonates have emerged as an important class of building blocks over the past three decades [1, 2]. Several of these compounds also exhibit interesting biological properties. Although numerous synthetic methods have been described for their preparation, they often involve tedious procedures. Therefore, there is still a lack for simple protocols leading to functionalized vinylphosphonates. We will describe here the synthesis of such compounds, using an original organocatalyzed substitution reaction of acetate group in diethyl (αacetoxymethyl)vinylphosphonate 1, in the presence of DABCO (1,4-diaza bicycle [2.2.2]octane) as organocatalyst, and under mild conditions. The other interest of this procedure is that the reaction can be run in water as solvent, thus expanding easily the use of nucleophiles to ionic salts.