The morphology, structure and melting behaviour of cold-crystallized isotactic polystyrene (iPS) were studied by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS). The polymer was found to crystallize according to the dual-lamellar stack model. The two populations of lamellae, along with a melting-recrystallization phenomenon, determined the appearance of multiple melting peaks in DSC traces. The annealing peak was attributed to the relaxation of a rigid amorphous phase, rather than to the melting of crystalline material.