The first experimental thermodynamic analysis of a metal organic framework (MOF) has been performed. Measurement of the enthalpy of formation of MOF-5 from the dense components zinc oxide (ZnO), 1,4-benzenedicarboxylic acid (H(2)BDC), and occluded N,N-diethylforrnamide (DEF) (if any) gave values of 78.64 +/- 2.95 and 99.47 +/- 3.62 kJ.[mol of Zn(4)O(BDC)(3)center dot xDEF](-1) for the as-made form and the desolvated structure, respectively. These as-made and desolvated enthalpies correspond to the values 19.66 +/- 0.74 and 24.87 +/- 0.94 kJ . (mol of Zn)(-1) respectively. The energetics of desolvated MOF-5 per mole of Zn falls in line with trends relating the enthalpy of inorganic porous materials (zeolites, zeotypes, and mesoporous materials) to molar volume. MOF-5 extends a plateauing trend first suggested by thermodynamic studies of mesoporous materials. This leveling off of the destabilization energetics as the void space swells suggests that additional void volume beyond a certain point may begin to act as a parameter "external" to the structure and not destabilize it further. This could help explain the rich landscape of large-volume MOFs and their ease of desolvation.