Time domain reflectometry (TDR) was used to examine the complex dielectric permitivity spectra (CPS) of binary mixtures of 1,4, and 1,3 butanediol (BD) with 1,4 Dioxane (Dx) at high frequencies (10 MHz-50 GHz). Both systems show the Cole-Davidson type of relaxation process. The least squares fit (LSF) method is applied to compute dielectric relaxation parameters from the CPS. The interest of the ongoing research is to understand the molecular associations, orientation of electric dipoles, and change in electric dipole density in the liquid mixture with the help of excess dielectric parameters, Bruggeman factor (f(B)) and the Kirkwood correlation factor for both systems.