We present a method for approximating thermodynamic parameters , ΔH, and ΔS for the cation exchange process in metal–organic frameworks, as exemplified by Ni²⁺ exchange into Zn₄O(1,4-benzenedicarboxylate)₃ (MOF-5) and Co²⁺ exchange into MOF-5 and Zn₅Cl₄(bis(1H-1,2,3-triazolo-[4,5-b],[4′,5′-i])dibenzo-[1,4]-dioxin)₃ (MFU-4l). For these examples, we find that the cation exchange process is endergonic and that parameters such as solvent and cation identity impact the thermodynamics.