The complex dielectric spectra of nitrobenzene, 2-butanol and their binary mixtures were measured in the frequency range of 10 MHz-20 GHz at different temperatures using Time Domain Reflectometry. The static permittivities and relaxation times were extracted from the complex dielectric spectra of the pure compounds and binary mixtures by fitting to the Debye model using the least-squares fitting method. The derived static permittivity (ε 0) and dielectric relaxation time (τ 0) values were used to calculate various dielectric parameters including the excess dielectric constant, effective Kirkwood correlation factor, excess inverse relaxation time and thermodynamic parameters. Excess dielectric parameters were fitted with the Redlich-Kister type polynomial equation. The result from dielectric analyses confirms the formation of a heterogeneous complex structure by association of unlike molecules. This hetero-molecule interactions produce a electric field in the mixtures and, as a result, the effective dipoles rotate faster. Molecular rotation and dipole reorientation motions in these complex system are discussed in terms of the molar activation entropy and enthalpy. Additionally, the hydrogen bond interaction between solute and solvent were confirmed by FT-IR spectral analysis. © 2016 Springer Science+Business Media New York.