Zirconium diethylene triamine pentamethylene phosphonic acid (ZrD) was synthesized and showed high adsorption capacity for Pb2+. Cross-linked ZrD nanocomposite Pb2+ selective membrane was prepared by sol¿gel using poly(vinyl alcohol) (PVA) as plasticizer in aqueous media. Developed ZrD nanocomposite membrane showed good thermal, mechanical and chemical stabilities, which are essential parameters for its durability. Furthermore, conductivity and counter-ion transport studies of these membranes suggested their potential application for separating Pb2+ by electrodialysis (ED). Electro-dialytic studies revealed very high Pb2+ flux across ZrD membranes in comparison with other bi-valent metal cations (Cu2+, Cd2+ and Ni2+). Relatively high retention of Pb2+ in the membrane phase was attributed to its controlled cross-linked structural morphologies, and completely intermingled and well connected network between the metal phosphonates and the polymeric backbone. Furthermore, high separation factor (2.0¿3.0) for separating Pb2+/Cu2+, Pb2+/Cd2+, and Pb2+/Ni2+, suggested practical applications of developed membrane for electro-dialytic fractionation/removal of Pb2+ from industrial waste water.