The complexation of bile acids with various solvated polycations was studied. A one-to-one complex was precipitated when an aqueous solution of cholic acid sodium salt (CA) was mixed with aqueous solutions of 3,3-ionene and grew to form crystals with needle-like morphology, 3 millimeters in length. Hydrogen bonding of hydroxyls at the steroid face and the spacing between cationic sites of polycations were crucial for the formation of the giant needle.