Local polymer dynamics are studied in polymers bearing dipoles rigidly attached to the backbone. The compounds are based on cyano-substituted dihydrobenzimidazoles bearing ultrastrong dipole moments (similar to 12 D per repeat unit) incorporated in a poly-p-phenylene backbone, giving rise to polymers with rigid dipoles perpendicular to the chain. They belong to type B polymers according to the Stockmayer classification. They are ideal model systems for studying rotational isomers in the gas phase and the self-assembly and local dynamics in the solid state. Gas phase calculations (DFT) provided the dipole moments, the energetic barriers, and the backbone conformation as a function of the dipole strength and dipole separation. Calculated dipole moments show an odd even effect as a function of dipole separation. Specific rotational isomers that maximize the dipole moment are obtained. In the solid state, dielectric spectroscopy and site-specific NMR techniques revealed that packing through intermolecular forces such as van der Waals, pi-pi, and dipole-dipole interactions dictates the dynamics. Dielectric spectroscopy further identified two modes, both with Arrhenius temperature dependence and activation energies of 20-23 kcal/mol. Combined results attribute the faster process to a libration motion of the highly polar group reorienting only the nonplanar five-membered ring and the slower process to larger amplitude and/or correlated motions of the polar groups. These dynamic results are in agreement with structural investigations (X-ray diffraction) demonstrating that type B polymers in the bulk have rigid backbones.