The ordered alignment of liquid crystal molecules plays a critical role in the applications of their optical properties. Langmuir-Blodgett (LB) monolayer films of chiral nematic liquid crystal, 4-cyano-4′-pentylbiphenyl(5CB), doped with a proprietary left-handed chiral additive were prepared using stearic acid (SA) as template. The Langmuir isotherms of the chiral nematic liquid crystal at the CdCl2 interface with SA were studied. In the surface pressure curves, there was one sharp peak at the transition from gas phase to liquid phase. The phenomenon is considered to be the phase-separation of liquid crystals from SA. The chiral nematic liquid crystal multilayers LB films were characterized by ultraviolet-visible spectroscopy, X-ray diffraction, and atomic force microscopy. The results show that the chiral nematic liquid crystals were homogeneously and regularly dispersed in the SA template.