The ab initio intra- and inter-molecular potential energy surfaces (PESs) for the H 2 O-Ne system that explicitly incorporate the intramolecular overtone state ( v OH = 2) of H 2 O are presented. The electronic structure computations have been carried out at the explicitly correlated coupled cluster theory [CCSD(T)-F12] level with an augmented correlation-consistent triple zeta basis set and an additional bond function. The vibrationally averaged three-dimensional intermolecular potentials for |00 + 〉, |02 + 〉, |02 - 〉 and |11 + 〉 are obtained analytically by fitting to the multi-dimensional Morse/Long-range potential function form. These fits to 46 980 points have a root-mean-square (RMS) discrepancy of 0.12 cm -1 for interaction energies less than 1000.0 cm -1 . With the vibrationally averaged PESs for the H 2 O-Ne, we employed the combined radial discrete variable representation/angular finite basis representation method and Lanczos algorithm to calculate rovibrational energy levels ( J = 0-10, n s ≤ 2). The predicted infrared transitions and intensities of the para - and ortho -H 2 O-Ne complex are in good agreement with the available experimental data for |02 - 〉 ← |00 + 〉, |02 + 〉 ← |00 + 〉 transitions. In particular, the RMS discrepancy for |02 - 〉∑ e (0 00 ,0) ← |00 + 〉∑ e (1 01 ,0), including P and R branch patterns, is only 0.045 cm -1 , which is comparable with the experimental values. These results will provide reliable theoretical guidance for the future infrared overtone spectroscopy of clusters.