Differential scanning calorimetry and broadband dielectric spectroscopy measurements were performed to investigate the phase transitions in nematic liquid crystal (LC)/benzene mixtures. Noticeable changes of the crystal-isotropic phase transition and the phase transition enthalpy were observed. We also estimated the number of unfreezable benzene molecules from the LC/benzene mixtures. The crystal-isotropic phase transition temperature was described very accurately from the temperature-dependent relaxation strength, the relaxation time, and the symmetric shape parameter obtained from the fitting procedure. Surprisingly, the abnormal behavior of the isotropic phase was observed in LC/benzene mixtures that suggested the presence of local structure in the mixture, which set off the dipole moments along the long axis. The interaction between the LC molecules was also discussed from the tau-beta diagram.