The electrochemical reduction of pertechnetate ions (TcO4-) and properties of such formed reduced Tc containing species (ions and molecules) have been studied in strongly acidic media (4 + 12 M aqueous H2SO4) using electrochemical (cyclic voltammetry (CV); chronoamperometry (CA), chronopotentiometry (CP)) and spectro-electrochemical (UV-VIS OTTLE and Au-SERS) techniques. The results show generation of Tc(V) containing species in the first steps of the pertechnetate electroreduction. The experiments carried out in 6, 8 and 10 M H2SO4 have shown that an increase in the acid concentration shifts the Tc(VII) electroreduction wave towards positive potential values. Additional Au-SERS experiments indicate generation of Tc species with intermediate oxidation states (V) characterised by a band at 792 cm(-1) that are distinguishable from TcO2 or polymeric Tc(IV) forms. Application of derivative pulse techniques allows determination of pertechnetates in strongly acidic solutions at a level of 10(-6) mol/dm(3) even in the presence of impurities, such as. Fe3+ and Cl- , with concentrations comparable or greater than pertechnetates.