The sequential bond dissociation energies (BDEs) of Ba2+(H2O)(x) complexes, where x = 1-8, are determined using threshold collision-induced dissociation (TCID) in a guided ion beam tandem mass spectrometer. The electrospray ionization source generates complexes ranging in size from x = 6 to x = 8 with smaller complexes, x = 1-5, formed by an in-source fragmentation technique. The only products observed result from sequential loss of water ligands. Charge separation, a process in which both hydrated singly charged barium hydroxide and hydronium ion are formed, was not observed except for Ba2+(H2O)(3) yielding BaOH+ + H5O2+. Modeling of the kinetic energy- dependent cross sections, taking into account the number of collisions, energy distributions, and lifetime effects for both primary and secondary water loss, provides 0 K BDEs. Experimental thermochemistry for the x = 1-3 complexes is obtained here for the first time. Hydration enthalpies and reaction coordinate pathways for charge separation are also examined computationally at several levels of theory. Our experimental and computational work are in excellent agreement in the x = 1-6 range. The present experimental values and theoretical calculations are also in reasonable agreement with the available literature values for experiment, x = 4-8, and theory, x = 1-6. Of the numerous calculations performed in the current study, B3LYP/DHF/def2-TZVPP calculations including counterpoise corrections reproduce our experimental values the best, although MP2(full)/DHF/def2-TZVPP//B3LYP/DHF/def2-TZVPP results are comparable.