New mass-resolved two-photon spectra of NeXe involving molecular Rydberg states that dissociate to Ne+Xe*(6p) have been recorded using the combined techniques of (2+1) resonance enhanced multiphoton ionization and time-of-flight mass spectrometry. Excited state symmetries were deduced from separate spectra recorded with linearly and circularly polarized light. Vibronic analyses show that most of the excited states in this spectral region are essentially repulsive except for shallow minima whose electronic origins lie above their asymptotic dissociation limits. The magnitude of the potential humps for the excited states have been estimated. These results are rationalized in terms of an excited state bonding scheme that is dominated predominately by the interplay between repulsive exchange interactions and attractive long-range forces. (C) 1997 American Institute of Physics.