The effect of gamma radiation in vacuum on the isothermal crystallization kinetics of syndiotactic polystyrene (sPS) was investigated via differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and x-ray diffraction (XRD). Amorphous sPS samples were irradiated in vacuum, heated to 310 °C, cooled down to crystallization temperatures (Tcs) from 220 to 260 °C, and annealed for different times. Upon reheating, overlapping endothermic melting peaks depicted the various crystallization forms, α, β, and β′. The endotherms were resolved using Gaussian functions relating enthalpy changes to the endothermic envelope. Isothermal crystallization kinetic data were analyzed using Avrami's model with Gaussian functions. The extent of crystallization of β and β′ forms increased with increasing crystallization time and temperature, while that of α form decreased. Crystallization half-time followed a modified Arrhenius equation. Crystallization activation energies for the β and β′ forms of sPS increased with increasing radiation doses. The results are compared to those of air irradiated sPS reported in the literature.