We report here measurements of rovibrational levels in the electronic ground state of water at the previously inaccessible energies above 26,000 cm-1. The use of laser double-resonance overtone excitation extends this limit to 34,200 cm-1, which corresponds to 83% of the water dissociation energy. We use experimental data to generate a semi-empirical potential energy surface that now allows prediction of water levels with sub-cm-1 accuracy at any energy up to the new limit.