In order to explain the effect of structural factors on the physico-chemical properties of solid compounds based on biologically active cholate ion (Ch), three types of complexes (catanionic, metaloamphiphilic and hostguest) that show tendency to form supramolecular membranes were synthesized. Various experimental techniques were used: CHN analysis, NMR, IR spectroscopy, DSC, X-ray diffraction (WAXD and SAXD), microscopy (POM i SEM), and DFT calculations. Catanionic amphiphiles were sythesized by the interaction of sodium cholate (NaCh) and quaternary ammonium salts, by varying the number of n-dodecyl chains on the ionic group (nc), and the number of ionic groups (nh) in the molecule. The room temperature (RT) structure of catanionics is atipical bilayer, and smectic (Sm) at higher temperatures. The dependence of polymorphic and mesomorphic properties, thermodynamic parameters and bilayer thickness on nc and nh was studied. Metaloamphiphiles were sythesized by the interaction of NaCh with Ag(I), Ca(II), Ba(II) or La(III) salts, and by neutralization of Ag(I) oxide or Ca(II) hydro(oxyde) with cholic acid. Interaction of Ch and metal cation at higher concentration range results in gelation, and bidentante coordination of Ch. Addition of NaCh; sodium 4-(1-pentylheptyl)benzenesulfonate (NaDBS); n-dodecylsulfate (NaDS); potassium picrate (KP) into the 18C6 ether cavity forms hostguest complexes. The RT phases of addition complexes are bilayered, while mesophases are formed at higher temperatures, mostly Sm (18C6.NaDS i 18C6.NaDBS) or cholesteric (18C6.NaCh).