This work highlights the role of synthetic carrier (ionophore) in the separation of heavy metal ions. A new series of ionophores; 4,4′-nitrophenyl-azo-O,O′-phenyl-3,6,9-trioxaundecane-1,10-dioate (R1), bis[4,4′nitro-phenylazo-naphthyl-(2,2-dioxydiethylether)] (R2) 1,8-bis-(2-naphthyloxy)-3,6-dioxaoctane (R3), 1,11-bis-(2-naphthyloxy)-3,6,9-trioxaunde-cane (R4), 1,5-bis-(2-naphthyloxy)-3-oxa-pentane (R5) have been synthesized and used as extractant as well as carrier for the transport of various metal ions (Na+, K+, Mg2+, Ni2+, Cu2+ and Zn2+) through liquid membranes. Effect of various parameters such as metal ion concentration, ionophore concentration, liquid–liquid extraction, back extraction, comparison of transport efficiency of BLM and SLM and different membrane support (hen’s egg shell and PTFE) have been studied. In BLM ionophores (R2–R5) transport Zn+ at greater extent and the observed trend for the transport of Zn2+ is R2 > R4 > R3 > R5 respectively. Further transport efficiency is increased in SLM. In egg shell membrane ionophores (R2–R5) transport Zn+ due to their non-cyclic structure and pseudo cavity formation while ionophore R1 transports Cu2+ ions at greater extent due to its cyclic structure and cavity size. Among the membrane support used egg shell membrane is found best for the transport of zinc ions because of its hydrophobic nature and exhibits electrostatic interactions between positively charged zinc ions and –COOH group of egg shell membrane. Thus structure of ionophores, hydrophobicity and porosity of the membrane support plays important role in separation of metal ions.