An extraction chromatographic separation of U(VI), Th(IV), Np(IV), and Pu(IV) using polymer sorbents impregnated with acid type phosphorylpodand 1,5-bis[2-(oxyethoxyphosphinyl)-4-(ethyl)phenoxy]-3-oxapentan and its mixtures with quaternary ammonium base methyltrioctylammonium nitrate was performed. The effect of the stationery phase composition and nitric acid concentration on the sorption of the actinides was studied. A synergistic effect of sorbents containing mixtures of phosphorylpodand and methyltrioctylammonium nitrate on the extraction of the actinides was found. The results obtained provided a number of separation techniques for Np(IV), Pu(IV), Th(IV), and U(VI) in the processed products of spent nuclear fuel.