An analytical potential energy surface (PES) for the ground state of the [HeHNe]+ system has been constructed from a set of 19 605 ab initio data points, obtained from coupled cluster singles and doubles with perturbative triples correction calculations and the aug-cc-pVQZ basis set. The PES is based on the many-body expansion form proposed by Aguado and Paniagua (J. Chem. Phys. 1992, 96, 1265), and it has a root-mean-square error of 0.03 kcal/mol. The minimum energy pathways (MEPs) for different Ne-H-He angles are calculated, and it is found that the MEP for 180 (linear) goes through the deepest potential energy well. Preliminary quantum dynamical studies are performed for the He + NeH+ (v = 0-2, j = 0-3) → HeH+ + Ne reaction in the 0.0-0.5 eV collision energy range. Quantum calculations are carried out using a time-dependent wave packet method within the centrifugal sudden approximation. Reaction probabilities exhibit strong oscillatory behavior arising because of the metastable [HeHNe]+. Vibrational excitation has been found to enhance the reaction cross sections. © 2013 American Chemical Society.