Domestic wastewater treatment by purple phototrophic bacteria (PPB) is based on the assimilative uptake of organics and nutrients into the bacterial biomass. Thereby, it strongly depends on the carbon/nutrients ratio of the wastewater. The physiological COD/N/P ratio for PPB growth in domestic wastewater makes the addition of an external organic carbon source necessary in order to allow for an efficient process. However, PPB need a source of alkalinity (as CO2) to grow on reduced organics that serves as an electron acceptor since biohydrogen production (an alternative electron sink) is inhibited by ammonium. A preliminary experiment showed that high nutrients-loading wastewater was limited by CO2 imbalance, leading to poor removal efficiencies. Subsequently, the effect of the oxidation state of the organics added as external organic carbon sources to PPB reactors treating low nutrients-loading domestic wastewater has been analyzed. Three organics were used as additives to PPB development in four consecutive batches: acetate (more oxidized), ethanol and butyrate (more reduced). The PPB population was settled and the general performance under the three situations, in terms of organics, N and P assimilation, and growth kinetics was not significantly different irrespective of the external organic carbon source. The reactors were dominated by PPB, though reduced organics allowed for dominance of Rhodopseudomonas palustris, whereas oxidized organics caused co-dominance of R. palustris and Rhodobacter capsulatus. Thereby, alkalinity (as bicarbonate), and not the oxidation state of the organics, is the key parameter for the efficient treatment of domestic wastewater by PPB.