The extraction of technetium species at oxidation state lower than +7 has been examined in sulfuric and sulfuric/nitric acid solutions using UV–Vis spectroscopy and optically transparent thin layer cell (RVC-OTTLE). Soluble Tc(III), TcO2+ and [Tc2O2]3+ species with absorption bands at 420–450, 400, and 502 nm, respectively, were detected as products of pertechnetates electroreduction. The distribution ratios of 99Tc with lower than +VII oxidation state ionic species between 4 M H2SO4 and 30 % TBP/kerosene were found and are significantly lower than for TcO4 − in the same solution.