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The present study focuses on exploring the effects of reactivity and degree of dispersion of BaCO3 additions in the manufacture of sulfate-resistant OPC cements. A new electrochemical deposition method is attempted to effec- tively disperse BaCO3 particles (studying two different materials with particle size: D50 = 11.45 and 2.37 μm) on cement to enhance their reactivity and favour sulfate immobilisation in the form of BaSO4. The barium carbonate additions, particularly the finest, activate cement hydration to a greater extent. Electrodeposition is also observed to improve early age reactivity (2 d–7 d) in fine BaCO3. Cement paste bearing 15 wt % BaCO3 is more resistant to sulfate attack by a 5% (w/v) solution of Na2SO4 (180 d at 23 ◦C) than a commercial sulfate-resistant cement, although secondary ettringite and gypsum precipitated in all cases.