Technetium tribromide and triiodide were obtained from the reaction of the quadruply Tc-Tc-bonded dimer Tc-2(O2CCH3)(4)Cl-2 with flowing HX(g) (X = Br, I) at elevated temperatures. At 150 and 300 degrees C, the reaction with HBr(g) yields TcBr3 crystallizing with the TiI3 structure type. The analogous reactions with flowing HI(g) yield TcI3, the first technetium binary iodide to be reported. Powder X-ray diffraction (PXRD) measurements show the compound to be amorphous at 150 degrees C and semicrystalline at 300 degrees C. X-ray absorption fine structure spectroscopy indicates TcI3 to consist of face-sharing TcI6 octahedra. Reactions of technetium metal with elemental iodine in a sealed Pyrex ampules in the temperature range 250-400 degrees C were performed. At 250 degrees C, no reaction occurred, while the reaction at 400 degrees C yielded a product whose PXRD pattern matches the one of TcI3 obtained from the reaction of Tc-2(O2CCH3)(4)Cl-2 and flowing HI(g). The thermal stability of TcBr3 and TcI3 was investigated in Pyrex and/or quartz ampules at 450 degrees C under vacuum. Technetium tribromide decomposes to Na{[TC6Br12](2)Br} in a Pyrex ampule and to technetium metal in a quartz ampule; technetium triiodide decomposes to technetium metal in a Pyrex ampule.