The dielectric investigation has a great importance in liquid crystal studies as a supportive method to DSC for a complete characterization of liquid crystals as well as in the electronic applications. In this study, the synthesis, mesomorphic characterization and dielectric properties of a new phenylbenzoate-based three-ring calamitic liquid crystal which composed of ester linking groups,(S)-3,7-dimethyloctyloxychiral unit at one of terminals andn-octyloxy chain at the other end of the molecule, have been reported. The new calamitic liquid crystal 4-[4-((S)-3,7-dimethyloctyloxy)phenoxy)carbonyl]phenyl 4-(n-octyloxy)benzoate (DPCPB) has been characterized using(1)H,C-13-NMR and MS-QTOF. The liquid crystalline behavior of the target compound has been investigated by differential scanning calorimetry and optical polarizing microscopy. DPCPB exhibits an enantiotropic non-tilted smectic mesophase in a wide temperature range. The real and imaginary dielectric constant, conductivity mechanism, impedance and dielectric relaxation mechanism of DPCPB have been investigated depending on frequency at different temperatures.