The present study emphasizes the effect of addition of sodium citrate (C6H5Na3O7.2H2O) and sodium tungstate (Na2WO4.2H2O) to a silicate based electrolyte system on the corrosion behavior of PEO treated ZM21 magnesium alloy. The phase composition of the as-developed coating was evaluated by X-ray diffraction (XRD) analysis, while its surface morphology, thickness and elemental distribution were observed using scanning electron microscopy (SEM) and energydispersive spectroscopy (EDS). Potentiodynamic polarization tests were done in 3.5 wt% NaCl solution to analyze the corrosion behavior of the ceramic coatings in simulated marine environment. The results of XRD showed that the phase composition of all coatings comprised of Mg2SiO4 and MgO irrespective of the additive used. In addition to Mg, Si and O, the presence of W, C in EDS spectrum indicated that these elements were incorporated into the coating from the electrolyte system containing tungstate and citrate. The corrosion test results revealed that the PEO coatings obtained in tungstate containing electrolyte solution showed higher corrosion resistance than those formed in citrate containing electrolyte solution. © (2012) Trans Tech Publications.