In connection with the recent study of the ground electronic state of the LiH2+ molecular ion (Kraemer, W. P.; Spirko, V. Chem. Phys. 2006, 330, 190), the adiabatic three-dimensional double-minimum potential enery surface of the first excited electronic state was evaluated, including its two lowest atom diatom dissociation channels as well as the three-atom complete fragmentation asymptote. Applying the Sutcliffe-Tennyson Hamiltonian for triatomic molecules, the levels of all bound vibrational states and the levels of the states localized in the two energy minimum regions were separately determined. The validity of statistical methods such as the density of states approach and the nearest-neighbor level spacing distribution (NNSD) was tested for the light LiH2+ ion. Special effort was put into investigating possible effects of a tunnelling motion across the proton-transfer barrier on the vibrational level pattern using the NNSD approach.