The microwave dielectric relaxation behavior of binary mixtures of nitrobenzene with primary alcohols namely ethanol, 1-propanol and 1-butanol has been studied at different temperatures using Time Domain Reflectometry method. The measured complex dielectric spectra of pure and mixture solutions have been fitted with Debye model using least square method. The obtained static dielectric and relaxation time constant values are plotted against mole fraction of solute. The important dielectric parameters such as excess dielectric constant, excess inverse relaxation time and effective Kirkwood correlation factors are computed and the same has been used to interpret the intermolecular interaction and dynamic change in the solution. Furthermore, the mixing effect of nitrobenzene in different chain length alcohols has been explored by concentration dependent excess dielectric constant values. The positive molar enthalpy values of mixtures indicate that the heat energy is absorbed owing to the process of dipole reorientation. Moreover, the heterogeneous interaction between solute and solvent molecular functional groups has been confirmed by equi-molar FT-IR spectra analysis. © 2016