Apart from their biological importance, bile acids show interesting properties in their crystal form. Cholic acid (CA) is one of the best studied. Due to its unique amphiphilic form, in crystals CA assembles into bilayers. Special shape of CA molecules creates open cavities in the hydrophobic interfaces between bilayers. These cavities can have various shapes and sizes and can include other molecules as guests. Although guest molecules differ in chemical nature and size, some crystal packing features remain unchanged. The series of CA compounds with elongated guest molecules of varying length was crystallized to study packing arrangements. The obtained crystal structures are the first examples of CA cocrystals with guest molecules of comparable size. It was found that the typical bilayers are still present but in some cases previously unobserved arrangement is formed.