We report DNA thermotropic liquid crystal (TLC) formation by positively charged catanionic surfactant bilayer vesicles. The properties of DNA TLCs were found to be manipulated by both the chemical structures of cationic and anionic surfactants and the DNA amount. Positively charged catanionic bilayer vesicles bond to negative DNA sites resulting in the transition from vesicles to long range ordered lamellar crystals of DNA-catanionic surfactants, as confirmed by cryo- and freeze-fracture (FF) TEM observations and small-angle X-ray scattering (SAXS) measurements.