Twenty-two radiochemical separation procedures for neutron activation analysis (NAA) of environmental and biological samples are presented. They are currently applied in the context of trace metal research related to the protection of the environment and human health. The radiochemical procedures are related to the separations of the elements into groups which allow the determination of up to 50 elements in each sample or to specific separations for single elements. The experience gained in the application of these radiochemical separations over more than ten years allows us to consider them as reliable for sensitive determinations of trace metals in environmental and biological samples.