Excited levels of 186Re have been studied using results of the single γ-ray spectra measurements following the thermal neutron capture reaction. Energies and intensities of more than 500 γ-transitions have been obtained with the high-resolution crystal diffraction spectrometer GAMS5 of ILL. Most of the obtained intense γ-transitions have been placed in the 186Re level scheme. A number of new levels, as well as the depopulation for levels observed earlier in the 187Re(p,d)186Re reaction measurements have been proposed. Structure of 186Re levels is interpreted in terms of two-quasiparticle plus rotor coupling model and compared with that of the neighbouring doubly-odd nucleus 188Re.