CdTe-based polycrystalline solar cells are leading candidates for terrestrial photovoltaic applications. High efficiency devices have been obtained despite large lattice mismatch between hexagonal CdS and cubic CdTe. In the present work, CdS was deposited by chemical bath deposition on Si substrates, and CdTe was deposited by close spaced sublimation. The chemical nature of the CdS/CdTe interface, structural properties, and their dependence on the fabrication parameters, e.g., substrate temperature (475-600 degrees C) and postdeposition CdCl2 heat treatment, were analyzed. In addition, the effects of crystallinity of CdS on the interface structural defects were examined. Small spot energy dispersive spectroscopy of the interface revealed a considerable amount of sulfur in CdTe. The concentration of sulfur, in general, was higher ill the grains with higher density of structural defects and at the grain boundaries. The planar defect density in CdTe films increased with substrate temperature, whereas the threading dislocation density decreased. Interface analysis showed that the majority of the crystalline defects in the CdTe films deposited on CdS were generated at the interface. The crystallinity of CdS did not have a major influence on the interface defect generation.