The equilibrium distribution of the electrons in the catalyst-oligoester-acrylates system was investigated. It was found that equilibrium distribution of electron in this system is determined by the ratio of catalyst concentration and electron attracting groups and, furthermore, by the possibility of electron exchange between the phthalate and methyl methacrylate groups of oligoesteracrylates. It was concluded that the anionic polymerization process of oligoesteracrylates has some peculiarities which distinguishes it from the anionic polymerization of vinyl monomers. That can probably be considered as a result of the “oligomer” molecules comprising two electron attracting groups that have different electron affinities which are separated by the system of o-bonds.