The kinetics of structural relaxation in oxide systems containing complexing elements—boron and silicon— was studied by the potentiometric method. The effect of the nature and composition of the oxide electrolyte and the quenching temperature on the kinetic parameters of the anionic polymerization process was uncovered. Modeling of the relaxation processes in liquid borosilicates was conducted. Two kinetic schemes of structural relaxation, taking account of the slowness of the depolymerization of silicon oxide complexes and change of the coordination of boron, are examined. The influence of different physical and chemical factors on the rate of the relaxation processes and the equilibration time are analyzed.