In the region between 500 nm and 300 nm the electronic spectrum of [TeBr6]2− displays absorptions which are assigned to s → p transitions. At shorter wavelengths ligand-to-metal charge transfer (LMCT) bands appear. Irradiation of [TeBr6]2− in acetonitrile led to a reductive elimination according to the equation [TeBr6]2− → [TeBr4]2− + Br2. Upon LMCT excitation (λirr = 254 nm) the quantum yield was Φ = 1.3 × 10−2 but decreased when the light was absorbed by the longer-wavelength sp bands (Φ = 0.7 × 10−3 at λirr = 436 nm).