To develop an environmentally friendly and cost-effective water-based inorganic coating process for hydrophobic, polyolefin-based microporous separators, the effect of surfactants in an aqueous inorganic coating solution comprising alumina (Al2O3) on polyethylene (PE)-based microporous separators is investigated. By using a selected surfactant, i.e., disodium laureth sulfosuccinate (DLSS), the aqueous Al2O3 coating solution maintained a dispersed state over time and facilitated the formation of a uniform Al2O3 coating layer on PE separator surfaces. Due to the hydrophilic nature of the Al2O3 coating layers, the as-prepared, ceramic-coated PE separators had better wetting properties, greater electrolyte uptake, and larger ionic conductivities compared to those of the bare PE separators. Furthermore, half cells (LiMn2O4/Li metal) containing Al2O3-coated PE separators showed improved capacity retention over several cycles (93.6% retention after 400 cycles for Al2O3 coated PE separators, compared to 89.2% for bare PE separators operated at C/2) and rate capability compared to those containing bare PE separators. Moreover, because the Al2O3-coated layers are more thermally stable, the coated separators had improved dimensional stability at high temperatures (140 °C).