Measurements of dielectric constant and dielectric loss at various frequencies have been carried out on the title compound for the entire smectic range of temperature. Dielectric strength, distribution parameter, and activation energy as evaluated from the experimental data are reported in the article. To obtain a deeper insight, the intermolecular interaction between a pair of 6CB4HPD molecules has been analyzed using quantum mechanically optimized molecular geometry and electronic structure with the help of the Gaussian 03 program (Gaussian, Inc., Wallingford, CT) along with B3LYP/6-31G** basis sets. An attempt has been made to correlate the molecular structure, relative energy, and configuration of various interacting pairs and the observed experimental findings.