The biological treatment of groundwater is used primarily to remove electron donors from water sources, providing (biologically) stable drinking water, which preclude bacterial regrowth during subsequent water distribution. To the electron donors belong also the dissolved metal cations of ferrous iron and manganese, which are common contaminants found in most (anaerobic) groundwater. The removal of iron and manganese is usually accomplished by the application of chemical oxidation and filtration. However, biological oxidation has recently gained increased importance and application due to the existence of certain advantages, over the conventional physicochemical treatment. The oxidation of iron and manganese is accelerated by the presence of certain indigenous bacteria, the so-called "iron and manganese oxidizing bacteria." In the present paper, selected long-term experimental results will be presented, regarding the bioremediation of natural groundwater, containing elevated concentrations of iron and arsenic. Arsenic is considered as a primary pollutant in drinking water due to its high toxicity. Therefore, its efficient removal from natural waters intended for drinking water is considered of great importance. The application of biological processes for the oxidation and removal of dissolved iron was found to be an efficient treatment technique for the simultaneous removal of arsenic, from initial concentrations between 60 and 80 microg/l to residual (effluent) arsenic concentrations lower than the limit of 10 microg/l. The paper was focused on the removal of As(III) as the most common species in anaerobic groundwater and generally is removed less efficiently than the oxidized form of As(V). To obtain information for the mechanism of As(III) removal, X-ray photoelectron spectroscopy (XPS) analyses were applied and it was found that As(III) was partially oxidized to As(V), which enabled the high arsenic removal efficiency over a treatment period of 10 months.