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The double melting behavior of syndiotactic polystyrene (sPS) with β′-form crystallites was systematically investigated by several analytical techniques, including differential scanning calorimetry (DSC), polarized light microscopy (PLM), transmission electron microscopy (TEM), as well as wide-angle and small-angle X-ray scattering (WAXD, SAXS). For preventing the possible chain re-organization during intermediate melting, a high-energy electron beam (e-beam) radiation was carried out on the melt-crystallized samples to chemically cross-link the amorphous chains between lamellar crystals. The WAXD intensity profiles of the irradiated sPS samples revealed that no crystal transformation took place, and the crystallinity fraction remained unchanged for a received dose up to 2.4 MGy. As the received dose was increased, however, the high melting temperature peak was gradually diminished and finally disappeared after 1.8 MGy e-beam radiation, suggesting that the double melting phenomenon was mainly attributed to the melting/re-crystallization/re-melting behavior. The re-crystallization mechanism of sPS samples was studied using DSC and PLM to reveal the effects of heating rate and annealing temperature on the Avrami exponent and re-crystallization rate constant. In addition, the lamellar morphologies of the re-crystallized samples were also investigated by means of SAXS and TEM. With increasing heating rate or annealing temperature, the derived Avrami exponent was slightly decreased from 1.4 to 1.1; in comparison, the re-crystallization rate showed a shallow maximum at a rate of 10 °C/min, but it became evidently reduced at high annealing temperatures. Based on the morphological observations, we proposed that the re-crystallization of β ′ -form sPS crystals involved with the presence of broad lamellar thickness distribution as well as abundant irregular loose folding chains on the lamellar surfaces, which became tightened and crystallized into the un-melted lamellae when the neighboring thinner lamellae trapped in-between were melted. Thus, the high melting temperature is dependent on the average thickness of lamellae consisting of the un-melted lamellae developed initially and thickened ones associated with re-crystallization.