Four polymerized ionic liquids (PILs) were systematically designed to study the effect of polymer architecture and linker polarity on ion aggregation and transport. Specifically, linear and network PILs with the same ammonium cations (Am) and bis­(trifluoromethane)­sulfonimide (TFSI) anions were prepared by step-growth polymerization, and polarity was tuned by incorporating two precise linkers, either polar tetra­(ethylene oxide) (4EO) linker or nonpolar undecyl (C11) linker. The glass transition temperature (T g) substantially increased with the nonpolar C11 linker or upon cross-linking to form a network. The low wave-vector (q) ion aggregation peak from wide-angle X-ray scattering (WAXS) was not observable in the linear 4EO PIL, while it was most pronounced in the network C11 PIL. The network C11 PIL exhibited the strongest decoupling, where the ionic conductivity at T g is greater than 1 order of magnitude higher than the other PILs. This systematic comparison suggests that network structure and nonpolar linkers can promote both ion aggregation and ionic conductivity close to T g.