118-crown-6, one of the most relevant crown ethers, and sodium cholate, steroidal surfactant 2 classified as natural bile salt, are components of novel, synthesized coordination complex; 18-crown-3 6-sodium cholate (18C6·NaCh). Like crown ethers, bile salts act as building blocks in supramolecular 4 chemistry in order to design new functionalized materials with a desired structure and properties. In 5 order to obtain thermal behavior of this 1:1 coordination complex, thermogravimetry and differential 6 thermal analysis were used, as well as microscopic observations and differential scanning calorimetry. 7Temperature dependent infrared spectroscopy (IR) gave a detailed view into phase transitions. The 8 structures during thermal treatment were observed with powder X-ray diffraction, and molecular 9 models of the phases are made. 10Hard, glassy, colorless compound 18C6·NaCh goes through crystalline -crystalline 11 polymorphic phase transitions at higher temperatures. The room temperature phase is indexed to a 12 triclinic lattice, while in the high temperature phases molecules take randomly one of the two different 13 configurations in the unit cell, resulting in the 2-fold symmetry. The formation of cholesteric liquid 14 crystalline phase occurs simultaneously with partial decomposition, followed by the isotropisation 15 with simultaneous and complete decomposition at much higher temperature, as obtained by IR. The 16 results provide valuable information about the relationship between molecular structure, thermal 17 properties, and stability of the complex, indicating the importance of an appropriate choice of cation, 18 amphiphilic, and crown ether unit in order to synthesize compounds with desired behavior.