In the present paper the formation of Liesegang structures, i.e. the process of periodic deposition with the mutual diffusion of two reacting chemicals in the presence of an external constant electric field, is studied using numerical modeling. The mathematical model of the process consists of three differential equations of diffusion-reaction for the concentrations of the initial components and the resulting precipitate. The kinetics of sedimentation is described in accordance with the Ostwald’s supersaturation theory. The equations of the mathematical model in one-dimensional and two-dimensional statements were solved numerically using the control volume method using computer code written by the authors in the C ++ language. As a result of numerical simulation in the absence of an electric field, periodic structures were obtained formed of the precipitate, which qualitatively corresponds to the patterns observed in the experiments. It is shown that numerically obtained Liesegang rings satisfy the well-known laws: the ratio of the distances to neighbouring rings remains constant and there is a power dependence between the distances to the rings and the time of their formation. The influence of the ratio of the concentration of the starting substances and the electric field strength on the nature of the structures formed is investigated. It also has been shown that an increase in the electric field strength leads to an increase in the number of structures formed.