The transport phenomena across polymeric membrane may be enhanced by applying various strengths inside or outside the system. Recently, polymer inclusion membrane (PIM) has been considered one of the most popular methods that acts as a sink for the contaminant and immobilizes it. In the literature, there is no report about how to achieve the synthesis of multi-layer PIMs. In this paper, an improvement of a novel category of membrane without carrier for performing ion separation is reported. Different membranes were elaborated from binary mixtures of polymers, cellulose triacetate (CTA), polymethyl methacrylate (PMMA) and polyvinyl chloride (PVC) using 2-nitrophenyl octyle-ether (NPOE) as plasticizer and carrier in the same time, in order to increase specific interactions between the different polymers. The membranes (Polymer 1– NPOE – Polymer 2) were synthesized by phase inversion method modified by changing the procedure of a plasticizer/carrier addition and characterized by FTIR, TGA, SEM, zeta potential and contact angle. The CTA-based membranes exhibited well-defined pores partially filled with the second polymer and NPOE. Overall, our results showed that the addition of NPOE resulted in homogeneous membranes with modified physical properties, such as thickness, and hydrophobicity. A study of transport of Pb(II) using the synthesized membranes was studied. Dialysis experiments of lead ions across a polymeric membrane have shown that (CTA + NPOE + PMMA) and (PMMA + NPOE + PVC) membranes proved a good performance in one stage by fixing 12.15 and 25.31% of lead, respectively, without any additionally added carrier and acids. These results confirm the affinity between a basic polymer (poly-methyl methacrylate) and the metallic ion (Pb2+).