A new radiochemical separation scheme based on extraction chromatography has been proposed for isolation of arsenic from selenium. The distribution coefficients of As and Se on prepared sorbents: (selected aromatic o-diamines supported on polystyrene adsorbents) were determined in order to find the best condition for separation of both the elements. Batch experiments were verified by column studies. This work, together with earlier results from this Laboratory, enabled to elaborate a new separation scheme for selective and quantitative separation of arsenic from selenium. Proposed approach insures high selectivity and radionuclide purity of separated arsenic fraction; it is also characterized by high elution efficiency (>95%) using small volume (2mL) of 0.9% NaCl with very low breakthrough (<0.01%) of selenium.