Abstract: The extraction-spectrophotometrical analysis of technetium in HLLW is described. First. Tc is extracted from the Na_2CO_3 medium into the 2.4, 6-trimethyipyridine and stripped into H_2SO_4 solution from the organic phase by the addition of CCl_4, then Tc is extracted into tetraalkylammonium (7402)/n-butyl chloride. The n-butyl chloride phase contacts with H_2SO_4 solution containing KSCN. and the purplish red complex with peak of absorption at 512nm is stable for several hours. The method was used for the determination of content of technetium in HLLW. and the result showed that many metal ions in it don't cause interfere with analysis of Tc.