Electroosmotic flow (EOF) involving displacement of multiple fluids is employed in micro-/nanofluidic applications. There are existing investigations on EOF hysteresis, i.e., flow direction-dependent behavior. However, none so far have studied the solution pair system of dissimilar ionic species with substantial pH difference. They exhibit complicated hysteretic phenomena. In this study, we investigate the EOF of sodium bicarbonate (NaHCO3, alkaline) and sodium chloride (NaCl, slightly acidic) solution pair via current monitoring technique. A developed slip velocity model with a modified wall condition is implemented with finite element simulations. Quantitative agreements between experimental and simulation results are obtained. Concentration evolutions of NaHCO3–NaCl follow the dissimilar anion species system. When NaCl displaces NaHCO3, EOF reduces due to the displacement of NaHCO3 with high pH (high absolute zeta potential). Consequently, NaCl is not fully displaced into the microchannel. When NaHCO3 displaces NaCl, NaHCO3 cannot displace into the microchannel as NaCl with low pH (low absolute zeta potential) produces slow EOF. These behaviors are independent of the applied electric field. However, complete displacement tends to be achieved by lowering the NaCl concentration, i.e., increasing its zeta potential. In contrast, the NaHCO3 concentration has little impact on the displacement process. These findings enhance the understanding of EOF involving solutions with dissimilar pH and ion species.