Nylon-6-clay hybrid (NCH) is a molecular composite of Nylon-6 and uniformly dispersed silicate monolayers of montmorillonite. In this study, orientation of montmorillonite and Nylon-6 crystallites in the NCH film was measured by x-ray diffraction and transmission electron micrography (TEM), which revealed that, the silicate layers and the Nylon-6 crystallites (gamma-form) have planar orientation, independent of montmorillonite content. Based on the crystal structure model proposed by Bradbury et al., it seems that hydrogen bonded sheet plane { 020 } or zigzag plane of molecular backbone {110} is parallel to the film surface. In contrast, crystallites in pure Nylon-6 film are randomly oriented. The degree of orientation of Nylon-6 crystallites increases with content of montmorillonite.