166Re reaction. Prompt γ rays were detected by the JUROGAM II γ-ray spectrometer, and the recoiling fusion-evaporation products were separated by the recoil ion transport unit (RITU) gas-filled recoil separator and implanted into the Gamma Recoil Electron Alpha Tagging spectrometer located at the RITU focal plane. The tagging and coincidence techniques were applied to identify the γ-ray transitions in 166Re, revealing two collective, strongly coupled rotational structures, for the first time. The more strongly populated band structure is assigned to the πh11/29/2−⊗νi13/21/2+ Nilsson configuration, while the weaker structure is assigned to be built on a two-quasiparticle state of mixed πh11/29/2−⊗ν[h9/2f7/2]3/2− character. The configuration assignments are based on the electromagnetic characteristics and rotational properties, in comparison with predictions from total Routhian surface and particle-rotor model calculations.