Polymer inclusion membranes (PIMs) based on cellulose triacetate (CTA) and dibutyl butyl phosphonate (DBBP) were tested for arsenic(V) separation from H2SO4 for its recovery from copper electrolytes. Solvent extraction experiments allowed the determination of the As(V)-DBBP and H2SO4-DBBP complexes formed in the organic phase. Application of a transient model to membrane transport experiments in solutions containing only arsenic or H2SO4 indicated that it occurred under a kinetically controlled regime by formation of H3AsO4[DBBP]2 and H2SO4[DBBP] species, respectively. When arsenic and H2SO4 are simultaneously present, the existence of a third species, H3AsO4[DBBP][H2SO4], explains well the fact that As(V) flux decreases and that H2SO4 flux increases. In both cases, a limiting 50% recovery value was obtained. However, active arsenic transport (>50%) is achieved if the H2SO4 concentration gradient is assured (e.g., using a triple-cell configuration). In this way, high arsenic recovery factors (90% in 800 min) were obtained with initial concentrations of 5000 mg/L As(V) and 220 g/L H2SO4. In all membrane systems tested, good As(V) selectivity over copper (up to 30000 mg/L) was attained.