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Abstract Electroosmosis on nonuniformly charged surfaces often gives rise to intriguing flow behaviors, which can be utilized in applications such as mixing processes and designing micromotors. Here, we demonstrate nonuniform electroosmosis induced by electrochemical reactions. Water electrolysis creates pH gradients near the electrodes that cause a spatiotemporal change in the wall zeta potential, leading to nonuniform electroosmosis. Such nonuniform EOFs induce multiple vortices, which promote the continuous accumulation of particles that subsequently form a colloidal band. The band develops vertically into a “wall” of particles that spans from the bottom to the top surface of the chamber. Such a flow‐driven colloidal band can be potentially used in colloidal self‐assembly and separation processes irrespective of the particle surface properties. For instance, we demonstrate these vortices can promote rapid segregation of soft colloids such as oil droplets and fat globules.