Thermal transitions of the three crystalline phases (gamma, delta, and epsilon) of syndiotactic polystyrene (s-PS), presenting s(2/1)2 helices, have been compared by X-ray diffraction, differential scanning calorimetry (DSC), and dynamic-mechanical analyses. These analyses have been conducted on crystalline (delta and epsilon) films. obtained by similar solvent sorption and desorption procedures, starting from a same gamma-form film. The Fourier transform infrared (FTIR) spectra of the three films have also been compared. The obtained results indicate that the recently discovered epsilon-phase, as the already known delta-phase, is transformed in gamma-phase by heating above 100 degrees C. However. the epsilon (->) gamma transition occurs directly without the formation, for intermediate temperatures, of a helical mesomorphic phase, as instead observed for the delta (->) gamma transition. DSC studies and FTIR measurements also suggest that the crystalline packing of the E-form could be rather similar to that one of the gamma-form.