Abstract Excited states of ²⁰⁶Rn have been studied via the ¹⁹⁷Au(¹⁴N, 5n)²⁰⁶Rn fusion reaction at a beam energy of 78 MeV. A number of transitions and levels are identified by the γ-γ coincidence measurement, further enriching the level scheme of ²⁰⁶Rn. Both the full configuration shell model and the nucleon-pair approximation (NPA) were utilized to investigate the single-particle configurations and seniority structures in ²⁰⁶Rn. The results of these two calculations suggest that the 2₁ ⁺ and 4₁ ⁺ states exhibit only a 50% component of a seniority-two state associated with a broken neutron pair. The collectivity of these two states primarily arises from configuration mixing due to residual proton-neutron interactions. The 6₁ ⁺ and 8₁ ⁺ states are predominantly characterized by a seniority-two state marked by a broken proton pair.