The two-photon resonant, three-photon (2+1) ionization spectra of jet-cooled (XeXe)-Xe-m-Xe-n, at energies near the Xe* 5d[5/2](0)(3) state, are reported. A new progression has been observed and is attributed to transitions from the van der Waals ground state, X(1) Sigma(g)(+)(0(g)(+)), through bound vibrational levels of an excited state of gerade symmetry. The analysis of some 26 closely spaced vibronic bands and isotope effects provides information on the excited and ground state potential energy curves. The vibrational quantum number of the lowest frequency band near 82 539.1 cm(-1) is assigned to upsilon’=6+/-1. For upsilon’=6 this leads to molecular constants T’(e) congruent to 82 514.9 cm(-1), omega’(e) congruent to 5.7955 cm(-1), and omega(e)x’(e) congruent to 0.07491 cm(-1). The upper state can be described by a morse potential with dissociation energy D’(e) congruent to 112.10 +/- 0.05 cm(-1) and internuclear separation R’(e) congruent to 5.51 +/- 0.03 Angstrom. This is consistent with assignment to a rydberg molecular state of either the B (II1/2g)-I-2 or D (2) Sigma(1/2g)(+) ion core. At the Xe S-1(0)+Xe* 5d[5/2](0)(3) threshold the molecular spectrum terminates and continuum absorption is evidenced by a rise and fall in the fragment ion yield. The direct determination of the dissociation limit for the excited state is used to derive the ground state dissociation energy D"(e) congruent to 196.32 +/- 0.05 cm(-1).