Selenium 79 is a beta emitter produced from (235)U fission and is one of the long half-life radionuclides of interest in nuclear waste disposal problematic because of its potential migration capacity to the surface environment. Measurement of (79)Se is particularly difficult due to its low activity in waste matrices (about 10(-3)Bqg(-1)). A radiochemical procedure based on ion exchange separations was already described in a previous paper. This work presents different applications of the radiochemical separation to waste samples and an improvement of this procedure, including a selective extraction of selenium as diethylselenium in an organic solvent followed by a re-extraction in aqueous medium. This additional step allows the decontamination factor to be increased with the aim of counting (79)Se by liquid scintillation counting.