The extraction of total arsenic and selenium using hollow-fibre supported liquid membranes (HFSLMs), with specific interest in the optimal conditions for the extraction in wastewater, is reported. The extraction time, type of liquid membrane, sample and donor pH and stirring rate were optimised, and thereafter, the developed method was tested in real wastewater samples. The optimal HFSLMs adopted, after optimisation tests, comprised of Aliquat 336, 0.8 M NaOH, 200 rpm and 80 min as the extractant, stripping phase, stirring rate and reaction time, respectively. The developed method had reasonable-to-high extraction efficiencies in real wastewater samples with the final effluent recording as high as 73 and 78 % removal efficiencies for Se and As, respectively. Considering the initial concentrations found in the samples, use of this developed method could bring down the concentrations to levels admissible by the United States Environmental Protection Agency (US-EPA) and World Health Organisation (WHO).