Electrokinetic transport of a charged dye within a free liquid film stabilized by a cationic surfactant, trimethyl(tetradecyl)ammonium bromide, subjected to an external electric field was investigated. Confocal laser scanning microscopy was used to visualize fluorescein isothiocyanate (FITC) separation within the stabilized liquid film. Numerical simulations were performed using the finite element method to model the dynamics of charged dye separation fronts observed in the experiments. Because of the electrochemical reactions at the electrodes, significant spatial and temporal pH changes were observed within the liquid film. These local pH changes could affect the local zeta potential at the gas-liquid and solid-liquid film boundaries; hence, the flow field was found to be highly dynamic and complex. The charged dye (FITC) used in the experiments is pH-sensitive, and therefore, electrophoresis of the dye also depended on the local pH. The pH and the electroosmotic flow field predicted from the numerical simulations were useful for understanding charged dye separation near both the anode and the cathode.