The condensation mechanisms of tetravalent technetium in chloride media were studied in the pH range 0–1.5. A new dimer complex of Tc(IV) has thus been discovered, Tc2OCl104−. Spectroscopic and kinetics studies showed that the formation of this compound resulted from the condensation of TcCl5(H2O)−. An EXAFS study indicates that the dimer displays a [Tc-O-Tc]6+ structure. As the pH increases, UV-visible measurements showed a cyclization of [Tc-O-Tc]6+ into [Tc(μO)2Tc]4+ leading, in fine, to the precipitation of TcO2·x H2O. The aquation constant (Kaq) of TcCl62− into TcCl5(H2O)− and the dimerisation constant (logKdim) of TcCl5(H2O)− into Tc2OCl104− were determined to be 2.20±0.26 and 4.68±0.09, respectively.