Simultaneous production of carrier-free radioisotopes, Zn-65 and Ga-66,Ga-67,Ga-68, has been achieved by activation of a thick copper target with a 50 MeV alpha-particle. A liquid-liquid extraction procedure for the effective separation of radionuclides Zn-65 and Ga-66,Ga-67,Ga-68 formed, respectively, through the nuclear reactions, (alpha, pxn) and (alpha, xn), from the target element has been developed in an aqueous hydrochloric acid medium using a liquid anion exchanger, trioctylamine (TOA), as an extractant. The extent of the separation and purity of the carrier-free radiotracers at different stages of their LLX separation has been verified by taking recourse to gamma-ray spectrometry. Copyright (C) 1997 Elsevier Science Ltd