The molecular chain conformation of the dried gel of syndiotactic polystyrene (sPS) in octadecyl benzoate solution was investigated. sPS gels form rapidly through solid-liquid phase separation. The obtained sPS chains are in the highly ordered all-trans TT skeletal conformation which is different from a twofold TTGG helical conformation that sPS assumes in normal solvents. The size of the solvent molecule is considered to play an important role in the formation of the conformation of sPS in solution.