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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 <i>Rhodopseudomonas palustris</i>, whereas oxidized organics caused co-dominance of <i>R. palustris</i> and <i>Rhodobacter capsulatus</i>. 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.