Abstract A network approach has been used to analyse the electrical properties of a classical symmetric electrochemical cell, i.e. a 1:1 binary electrolyte in a cell between two metal-parent-type electrodes. A network model for the Nernst-Planck and Poisson equations describing the ionic transport through the electrolyte solution and for the Butler-Volmer equations describing the interfacial kinetics in such a system has been proposed. With this model and the electric circuit simulation program pspice, the transient response of the system to a step-function-applied potential difference and the small-signal a.c. response of the system subject to a steady external voltage bias have been simulated. The study is intended mainly to emphasize the characteristics of the non-equilibrium electrical double layers at the electrode¦electrolyte solution interfaces and the overlapping effects between these space charge regions.