The dielectric behaviour of isobutanol and octanol with dibutyl phthalate have been studied at microwave frequency (9.36 GHz) at three different temperatures 303 K, 308 K and 313 K. Different dielectric quantities like dielectric constant (ε′), dielectric loss (ε″), static dielectric constant (ε 0) and dielectric constant at optical frequency (ε α) have been determined. These values are used to evaluate the relaxation time (τ) and dipole moment of the mixture. The relaxation time is calculated by both Higasi's method and Cole-Cole method. The results are discussed to interpret molecular structure in terms of relaxation time and excess dipole moment in the medium. The complex system investigated shows maximum relaxation time values as the concentration of the solute increases as well as the temperature increases.