Analyses of the effects of montmorillonite (clay) on the crystallinity and crystallization behavior of syndiotactic polystyrene (s-PS) were investigated by Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). The dispersibility of the clay in s-PS nanocomposites was studied by X-ray and transmission electron microscopy (TEM). The clay was dispersed into the s-PS matrix by melt blending on a scale of 1-2 nm or few tenths-100 nm, depending on the surfactant treatment. On adding clay, the crystallization behavior of the s-PS tends to convert into the beta-crystal from the alpha-crystal after being cold-crystallized because the clay plays a vital role in facilitating the formation of the thermodynamically favored beta-form crystal when the s-PS is cold- or melt-crystallized. This phenomenon leads to a change in a conventional mechanism of molecular packing for the s-PS. Evidently, the clay significantly affects the crystallinity and crystallization behavior of the s-PS.