A mathematical and computational model described in the previous paper (Gaš, B., Coufal, P., Jaroš, M., Muzikář, J., Jelínek, L., J. Chromatogr. A 2001, 905, 269–279) is adapted, algorithmized, and a computer program PeakMaster having a status of freeware (http://natur.cuni.cz/∼gas) is introduced. The model enables optimization of background electrolyte (BGE) systems for capillary zone electrophoresis. The model allows putting to use uni‐ or di‐ or trivalent electrolytes and allows also for modeling highly acidic or alkaline BGEs. It takes into account the dependence of ionic mobilities and dissociation of weak electrolytes on the ionic strength. The model calculates the effective mobility of analytes and predicts parameters of the system that are experimentally available, such as the transfer ratio, which is a measure of the sensitivity in the indirect UV detection or the molar conductivity detection response, which expresses the sensitivity of the conductivity detection. Further, the model enables evaluation of a tendency of the analyte to undergo electromigration dispersion or peak broadening. The suitability of the model is verified by comparison of the predicted results with experiments, even under conditions that are far from ideal (under extreme pH and a high ionic strength).