Guest molecular dynamics related to the stable complexing behavior of syndiotactic polystyrene (sPS)-xylene isomer (m-and p-xylene, abbreviated MX and PX) complexes have been characterized by solid-state C-13-NMR spectroscopy. Similar chemical shifts are observed for both sPS complexes in the C-13-CP/MAS spectrum. Interestingly, the solvent resonance of methyl carbon could be observed under CP conditions, indicating the relative rigidity of the solvent. Inversely, the sPS-MX system showed doublet peaks at 21.8 and 23.2 ppm when compared with the atactic PS-MX system, suggesting the orderly arrangement of the methyl group in the complexed system. The mobility of the guest molecule in the system is evaluated using spin-lattice relaxation time (T,,). Moreover, the mobility of helical chains of sPS is also inferred from its (T-1(c)). Hence, the influence of the mobility of the methyl carbon of xylene and the sPS helical chain could be investigated, which helps in studying the complexing behavior of the sPS-xylene system.