In this study, the relationship between chemical structure, nanoscale organization, and ion transport in 1,2,3-triazolium polymerized ionic liquids (PILs) was investigated by wide-angle X-ray scattering (WAXS) and broadband dielectric spectroscopy (BDS). Analyzing the WAXS and BDS results indicated that mobile ion types and chemical structure of the pendant groups controlled structural heterogeneity and ion conduction of the PILs below T_g. The normalized heterogeneity length extracted from WAXS data was used to correlate the structural heterogeneity and ion conduction activation energy. For the polycation samples, larger TFSI^– mobile anion results in a higher packed structure than small Cl^– while in the polyanion samples inverse trend was observed. The calculated activation energy of the dc conductivity below T_g is quantitatively correlated to the structural heterogeneity obtained from nano structure analysis using WAXS. This suggested increasing the spatial heterogeneity of the PILs results in the reduction of the activation energy of long-range ion motions. These results highlight the role of spatial heterogeneity in designing efficient polymerized ionic liquids