Radiochemical neutron activation analysis (RNAA) procedures for determination of Re at the ultratrace level based on use of liquid-liquid extraction (LLE) and extraction chromatography (EXC) have been developed. Two different LLE procedures were used depending on the way of sample decomposition using either 2-butanone or tetraphenylarsonium chloride in CHCl3. EXC employed new solid extractant materials prepared by incorporation of the liquid trioctyl-methylammonium chloride into an inert polyacrylonitrile matrix. The RNAA procedures presented have been compared and applied for Re determination in several biological and environmental reference materials.