Dipolar microstructure is a property related to the orientation of dipole moments along a polymer chain, which is dependent on how asymmetric monomers are oriented (i.e., regio-order). The control over the dipolar microstructure offers the possibility to monitor single-chain behavior in an electric field thus providing important structural and dynamical information. Using broadband dielectric spectroscopy (BDS), in this study, we first demonstrate that the initiation of glycidyl phenyl ether with the t-BuP4 phosphazene base and water leads to the formation of a polyether composed of two symmetric regioregular subchains with an opposite dipole moment orientation. After modification of hydroxyl end groups into alkyne, macrocyclic poly(glycidyl phenyl ether)s with an inverted-dipole microstructure were synthesized via Glaser coupling. The macrocycles obtained using this strategy display a dielectric normal mode relaxation that specifically reflects the fluctuations of the ring diameter. This important characteristic allowed us to evaluate the macrocyclic chain dynamics by BDS resulting in a dipole relaxation of the ring diameter 1.6 times slower compared to the analogous relaxation in the inverted-dipole linear precursor. These results highlight two main points, the power of BDS in the verification of architectural features of polymers having a net dipole moment component along the chain contour, and the potential of inverted-dipole macrocycles in the study of fundamental physical problems in polymer rings.