We provide an overview of the effect of the molecular structure on the dielectric properties of dimers exhibiting nematic and twist-bend nematic phases with special focus on how the conformational distribution changes are reflected by the dielectric behaviour. Nematic dimers show distinctive dielectric properties which differ from those of archetypical nematic liquid crystals, as for example, unusual temperature dependence of the static permittivity or dielectric spectra characterised by two low-frequency relaxation processes with correlated strengths. The interpretation of such characteristic behaviour requires that account is taken of the effect of molecular flexibility on the energetically favoured molecular shapes. The anisotropic nematic interactions greatly influence the conformational distribution. Dielectric behaviour can be used to track those conformational changes due to dependence of the averaged molecular dipole moment on the averaged molecular shape. Results for a number of dimers are compared and analysed on the basis of the influence of details of the molecular structure, using a recently developed theory for the dielectric properties of dimers.