Barium tungstate crystallites with different sizes and morphologies were successfully synthesized using a simple electro-chemical technique by varying the components of electrolyte solutions. XRD analysis evidenced that the as-prepared samples were a pure tetragonal-phase of BaWO4 with a scheelite structure. Scanning electron microscopy images and PL spectra of BaWO4 crystallites revealed that the presence of OH-ions and the incorporation of absolute ethanol into the electrolyte solution would have important effects on their particle sizes, morphologies, and optical properties.