The electromigration of liposomes is a complex process resulting in many unexpected behaviors that are difficult to address with existing theories. In this study, the electrophoretic behaviors of liposome populations under various conditions were examined through the use of capillary electrophoresis and the results compared to classical electrokinetic, colloid, and spheroid theories. To elucidate the possible effects of applied field strength, bilayer rigidity, and surface charge on these behaviors, the electrophoretic mobilities of liposome populations were monitored while varying the applied potential, ionic strength of the medium, and the surface charge and cholesterol content of the liposomes. On the basis of comparisons made to the theoretical predictions, our results suggest that liposomal deformation and field-induced polarization may occur during electrophoresis and these mechanisms help to describe many of the observed behaviors.