We report a comprehensive dielectric characterization of a liquid crystalline binary mixture composed of the symmetric mesogenic dimer CB7CB and the nonsymmetric mesogenic dimer FFO9OCB. In addition to the high-temperature nematic phase, such a binary mixture shows a twist-bend nematic phase at room temperature which readily vitrifies on slow cooling. Changes in the conformational distribution of the dimers are reflected in the dielectric permittivity and successfully analyzed by means of an appropriate theoretical model. It is shown that the dielectric spectra of the mixture reflect the different molecular dipole properties of the components, resembling in the present case the characteristic dielectric spectra of nonsymmetric dimers. Comparison of the nematic and twist-bend nematic phases reveals that molecular dynamics are similar despite the difference in the molecular environment.