The stability of Pickering emulsions depends on interfacial coverage of the emulsion droplets. Since, the interfacial thickness of water-water interface is very high, particles of comparable thickness can stabilize water-in-water (w/w) emulsions. To achieve this, mixture of oppositely charged particles are used, which are known to form large neutral aggregates and can be effective stabilizers for such emulsions. The w/w emulsions were formed by mixing PEO and dextran at different composition and the effect of surface charge of the particles on the kinetic stability of dextran-in-poly(ethylene oxide) (PEO) (D/P) emulsions was investigated. The phase preference of charged particles was also determined. The emulsions were visualized by confocal laser scanning microscope and characterized by drop size distribution and time evolution of drop size. It was found that negatively charged particles and mixture of oppositely charged particles (OCP) preferred the PEO phase and stabilize D/P emulsions. However, only the OCP were more effective stabilizers as they achieved complete interfacial coverage. © 2021 Taylor & Francis Group, LLC.