A hybrid liquid membrane process was used to remove cadmium cation from a solution using bis-(2-ethylhexyl) phosphoric acid as the carrier for the first time. Different polyethersulphone supporting membranes were prepared by a phase inversion technique. The prepared membrane could be efficiently used as the supporting membranes for the proposed process. The effects of porosity and pore size of the supporting membrane on removal efficiency were investigated. In addition, the effects of various operating parameters such as carrier concentration in organic phase, pH of feed phase, acid concentration, and temperature on the performance of the process were also investigated. It was found that the maximum flux of cadmium is obtained using the supporting membrane with 84.5% porosity and the pore size of 132 nm. The optimum carrier concentration is 0.2 M, the optimum pH of the feed phase is 6, and the optimum concentration of acid in the stripping phase is 0.6 M.