A solution containing ethanol as polar material and either benzene or n-dodecane as nonpolar solvent was heated by microwave irradiation employing a single-mode resonance microwave device. Although the microwave heating efficiency was expected from the just value of the relative dielectric constant (εr') or relative dielectric loss (εr″) for liquid system, it was revealed that the clustering structure of alcohol molecules expected from the excess parameter such as the excess relative dielectric loss is the important factor in the decision for efficiency of the microwave heating for the solution. This assumption and novel theory were strongly supported from the thermodynamic data such as vapor pressure and the partial enthalpy.