Defining the energetic landscape of pseudocapacitive materials such as transition metal layered double hydroxides (LDHs) upon redox-site enrichment is essential to harnessing their power for effective energy storage. Here, coupling acid solution calorimetry, in situ XRD, and in situ DRIFTS, we demonstrate that as the Ni/Al ratio increases, both as-made (hydrated) and dehydrated NiAl-LDH samples are less stable as evidenced by their enthalpies of formation. Moreover, the higher specific capacity at an intermediate Ni/Al ratio of 3 is enabled by effective water-LDH interactions, which energetically stabilize the excessive near-surface Ni redox sites, solvate intercalated carbonate ions, and fill the expanded vdW gap, paying for the "energetic cost" of being "redox-site-rich". Thus, from a thermodynamic perspective, engineering molecule/solid-LDH interactions on the nanoscale with confined guest species other than water, which energetically impose stronger stabilization, may help us to achieve their specific capacitance potential.