By adding a small amount of clay into poly(p-phenylene sulfide) (PPS)/polyamide 66 blends, the morphology was found to change gradually from seaisland into cocontinuity and lamellar supramolecular structure, as increasing of clay content. Clay was selectively located in the PA66 phase, and the exfoliated clay layers formed an edge-contacted network. The change of morphology is not caused by the change of volume ratio and viscosity ratio but can be well explained by the dynamic interplay of phase separation between PPS and PA66 through preferential adsorption of PA66 onto the clay layers and through layer-layer repulsion. This provides a means of manipulating the phase morphology for the immiscible polymer blends. The mechanical and tribological properties of PPS/PA66 blends with different phase morphologies (different clay contents) were studied. Both tensile and impact strength of the blends were found obviously increased by the addition of clay. The antiwear property was greatly improved for the blends with cocontinuous phase form. Our work indicates that the phase-separating behavior of polymer blends contained interacting clay can be exploited to create a rich diversity of new structures and useful nanocomposites.