We study the benzene-Rn (BzRn) complex in its electronic ground state using an ab initio scalar relativistic method in the framework of the coupled-cluster level of theory with single, double, and perturbative triple excitations [CCSD(T)]. Two different approaches to treat the scalar relativistic effects have been tested — the small-core pseudopotential (PP) and the Douglas–Kroll–Hess (DKH) Hamiltonian. These methods were used with the augmented Dunning’s double zeta basis set for C and H atoms, and the augmented triple PP basis set for Rn supplemented by midbond functions. Additionally, the effects of the basis extension for C and H atoms and the extension of the correlation space to include the internal orbitals of Rn and C have been tested. The comparison of the binding energy De and the equilibrium coordinate ze found with different methods has allowed to choose the optimal one based on PP for the construction of the analytical potential energy surface (PES). The long-range part of the potential has been fitted separately and the obtained long-range coefficients have been compared to their counterparts calculated from the first principles using the CCSD polarization propagator. The vibrational energy level pattern of BzRn has been studied, and the revealed polyad structure of the complex has been compared to the previously studied benzene-Kr and benzene-Xe complexes. A Python code that yields the interaction energy at any Rn position is provided.