Hydrochemical separation processes are one of the methods used for the treatment of spent nuclear fuel. Solvent extraction is also used in many other non-nuclear applications like the mining industry. In the nuclear case, hydrochemical separation processes are already employed in the world today for the recovery of uranium and plutonium. The method is however also considered for future separation systems for use in combination with the transmutation of the minor actinides. In a hydrochemical separation process the two phases are the pregnant (usually) aqueous feed and the organic phase comprising a diluent together with one or more extractants. One such class of extractants developed for partitioning and transmutation purposes is the bis(triazine)-bipyridine-type (BTBP) molecules. When assessing the feasibility and loading properties of such an extraction system, the solubility of the ligands is of the outmost importance. The understanding of whether the dissolution is enthalpically or entropically driven will also help the understanding of the differences in extraction observed between various diluents and temperatures. In this paper the enthalpy and entropy of dissolution of the BTBP-class ligands have been determined for different diluents. It has also been shown that it is possible to predict the extraction behavior of these molecules in the selected diluent once the solubility is known.