A systematic study was performed on the extraction and separation of uranium-cerium and thorium-cerium pairs for HDEHP from pure hydrochloric and sulphuric acid solutions as well as from their binary mixtures. The effect of water miscible alcohols and actone on the separation of these elements was also investigated. The separation of uranium and thorium from macroamounts of cerium can be best achieved from. 2.4 M HCl in presence of 50% isopropyl alcohol. There are other media plausible for the separation of trace cerium from uranium and thorium matrices.