Broadband dielectric spectroscopy (BDS) is a powerful technique that allows studying the molecular dynamics of materials containing polar entities. Among a vast set of different applications, BDS can be used as a complementary tool in polymer synthesis. In this work, we will show how BDS can be used to validate architectural features in Type-A polymers, those having a net dipole moment component along the chain contour. Specifically, we will focus on the evaluation of the dielectric relaxation of poly(glycidyl phenyl ether) (PGPE) samples designed and synthesized with a variety of topologies and regio-orders: linear regio-regular chains synthesized from monofunctional and bifunctional initiators, macrocyclic regio-regular chains, and linear and macrocyclic regio-irregular chains. Our study highlights the impact of using BDS as a complementary characterization technique for providing topological details of polymers, which are otherwise not possible with many traditional techniques (e.g., NMR and mass spectrometry).