Phase equilibrium (temperature-composition) relations of tetra-n-butylphosphonium formate (TBP-For), acetate (TBP-Ace), and lactate (TBP-Lac) semiclathrate hydrate systems have been measured. The highest equilibrium temperatures of TBP-For, TBP-Ace, and TBP-Lac semiclathrate hydrates were 280.9, 284.6, and 283.8 K at the atmospheric pressure, respectively, where the composition of tetra-n-butylphosphonium carboxylate was approximately 0.035 +/- 0.001 (mole fraction) in every system. The dissociation enthalpies of tetra-n-butylphosphonium carboxylate semiclathrate hydrates were measured by differential scanning calorimetry. The dissociation enthalpies of TBP-For, TBP-Ace, and TBP-Lac semiclathrate hydrates were (187 +/- 3), (193 +/- 3), and (177 +/- 3) J.g(-1), respectively.