We report the reduction of pertechnetate (Tc(VII)O 4 − ) to Tc(IV) species by bremsstrahlung irradiation of an aqueous solution of TcO 4 − at different pHs of the solution. When the TcO 4 − solution at pH 1.8 acidified with sulfuric acid was irradiated, soluble Tc(IV) species, which was proposed as polymeric Tc(IV) species, was formed. Amounts of the polymeric Tc(IV) species increased with an increase of absorbed dose and 80% of TcO 4 − was converted to the polymeric Tc(IV) species at 6.5kGy. By the irradiation of the TcO 4 − solution at pH 2.7, technetium(IV) oxide (Tc(IV)O 2 ·nH 2 O) colloids were formed in addition to the polymeric Tc(IV) species. At pH 4.1, only the Tc(IV)O 2 ·nH 2 O colloids were observed in the irradiated solution. The colloid particle was found as an aggregate (30–130nm) of tiny particles of 2–3nm in diameter. The polymeric Tc(IV) species was not filtered off with an ultrafilter (NMWL 10,000) and changed to TcO 2 ·nH 2 O colloids as the pH of the solution increased, suggesting that the polymeric Tc(IV) species was a precursor of TcO 2 ·nH 2 O colloids. The reduction of TcO 4 − in acidic media proceeds through a bimolecular reaction with hydrogen radicals (a product of water radiolysis) followed by successive disproportionation reactions of Tc(VI) and Tc(V).