Single-crystal structure determinations of all nine transition metal hexafluorides (Mo, Tc, Ru, Rh, W, Re, Os, Ir, and Pt) at -140 degrees C are presented. All compounds crystallize alike and have the same molecular structure. The bond length sequence r(w-F) congruent to r(Re-F) congruent to r(Os-F) < r(Ir-F) < r(Pt-F) is confirmed and paralleled by the sequence r(Mo-F) congruent to r(Tc-F) congruent to r(Ru-F) < r(Rh-F). Within the limits of precision, no systematic deviation from octahedral symmetry can be established. DFT and ab initio calculations predict octahedral structures for MoF6 and RhF6 and tetragonally distorted structures for ReF6 and RuF6. The energy barrier toward octahedral structures is only 2.5 kJ mol(-1) in the two latter cases. Calculated electron affinities are in the sequence MoF6 < TcF6 < RhF6 < RuF6 with a value of 6.98 eV for the latter. O2+RhF6-crystallized in an undisordered manner in P (1) over bar, isostructural to the low-temperature form of O2+AuF6-. RhF6- has a D-4h compressed octahedral structure, while AuF6- is essentially octahedral. The absorption spectrum of TcF6 and the F-19 and (NMR)-N-195 spectra of PtF6 are presented.