Abstract: The slovent extraction method of separating α nuclides from high level liquid waste (HLLW) is established by HDEHP, TiOA and TRPO. A separation procedure and analytical method for 237 Np, 239 Pu, 241 Am and all radioactivity of α nuclides in HLLW is recommended. The analysis results from HLLW show that the whole recovery is 88 %, 98 % and 99 % for 237 Np, 239 Pu and 241 Am, respetively.