To shorten the ripening period of filter sand, iron–manganese co-oxide filter film (MeOx) was formed quickly on the virgin quartz sand surface by oxidizing Mn2+ and Fe2+ from groundwater using KMnO4 continuously. After the start-up period, we found that Mn2+ could be removed efficiently by MeOx, even if the dissolved oxygen (DO) concentration in the influent was only about 1.0–1.5 mg/L. This means that the removal process of Mn2+ does not need to consume DO. The kinetic experiments for Mn2+ indicated that the adsorption and oxidation kinetics followed pseudo-first-order kinetics. The film (MeOx) was characterized by X-ray photoelectron spectroscopy (XPS). All manganese adsorbed on the surface of the sand was the oxidized form, and the manganese oxide coated onto the sand effectively oxidized Mn2+ to Mn3+ or Mn4+. The binding energy of the observed photoelectron peaks of O(1s) showed the existence of [≡Mn-OH] on the surface of the film by XPS, which might be a key intermediate in the mechanism of Mn2+ oxidation. Finally, a chemical catalytic oxidation mechanism for Mn2+ removal was proposed by the analysis of the oxidation process.