The ternary system of 4-cyano-4'-heptyl biphenyl (7CB), 4'-n-octyloxy-4-cyanobiphenyl (80CB), and Cholesteryl chloride (ChCl) exhibits very interesting unusual liquid crystalline phase of cholesteric, twisted grain boundary phase and re-entrant smectic-A phases, and it is obtained sequentially when the specimen is cooled from isotropic phase. These phases have been characterized by using X-ray and optical texture studies. The temperature variations of electrical conductivity and pitch of the cholesteric phase have been discussed.