Novel liquid crystalline polyesters of cholesterol, Polycholesteryl-3,3-dimethylacrylate (PCHDMA) and Polycholesterylcrotonate (PCHC) are synthesized by free radical polymerization and characterized by FT-IR, H-1-NMR, and GPC analysis. The thermal properties are studied by TGA and DSC techniques. The liquid crystalline phases are detected under hot stage optical microscope. Electronic conduction in the polymers is determined by Wagner polarization technique. There is about 5000 fold decrease in the impedance values of both PCHDMA and PCHC on increasing the frequencies from 40 Hz to 1 MHz at 30 degrees C. Amperometric analysis of the polymers are also carried out at different temperatures and frequencies.