In CZE one often gets more peaks than the number of sample components. In practice the additional peaks are often left unexplained or assigned to unidentified impurities or system peaks although cases exist when one analyte forms two or more regular distinct zones. One source of such effects are samples with high salt content that are generally assumed to bring higher sensitivity due to the sample self-stacking mechanism. The subject of this contribution is the theoretical and experimental investigation of the electromigration behavior of salt-containing samples. It is shown that they can exhibit splitting of the analyte zone into mutually independent parts detectable as well-developed distinct peaks. Theory based on velocity diagrams and computer simulations reveals that these effects originate in the transient phase of separation where electromigration dispersion profiles and sharp boundaries are formed and evolve. During this, the sample may induce parallel existence of several transient sharp boundaries (including system boundaries) that are simultaneously capable of stacking an analyte. Their electromigration is convergent and depending on whether they merge before the analyte destacks from them, permanent or transient double or multiple peaks are formed. Presented examples of anionic and cationic systems show good agreement with theory. The appearance of multiple peaks can be very variable, ranging from double or triple peaks to a major peak with a minor peak quite apart. Knowledge of the peak-splitting mechanism allows both to identify its presence in a given BGE and sample and to find effective remedy.