Blocky sulfonated syndiotactic polystyrene (SsPS) copolymers were produced using a recently developed postpolymerization functionalization procedure conducted in the gel state. The thermal properties and crystallization behavior of a matched set of blocky and random SsPS copolymers containing 3 and 10 mol% sulfonate groups were compared using differential scanning calorimetry (DSC), which shows that the blocky functionalization architecture displays a much faster rate of crystallization even at low sulfonate contents and a higher crystallizability at high sulfonate contents. The glass transition temperature for gelstate-functionalized copolymers was found to be independent of sulfonic acid content above 4% sulfonation, consistent with behavior observed in previous studies of sodium styrenesulfonate block copolymers. Small-angle X-ray scattering (SAXS) from the blocky copolymer indicates that the sulfonated units are distributed within the amorphous interlamellar domains. Wide-angle X-ray diffraction (WAXD) shows that the blocky architecture facilitates the formation of the beta form polymorph of sPS.