Rigid polyurethane foams were formed on rough zinc phosphate treated steel substrates. The interface between the two materials was investigated using knife peeling, immersion in a solvent which removes amorphous material predominantly, stud pull tests to observe bond failure, and X-ray scattering studies. There were three regions at the interface: an unbonded bare zinc phosphated surface, solid polyurethane areas where foaming did not occur, and foamed regions. These various interfacial regions result from temperature gradients during polymerization and foaming, and poor wetting of the substrate by the polymer. After immersion in a solvent, the solid polyurethane layer bonded to the substrate was completely removed, implying that this area only weakly adheres to the steel substrate. By contrast, the removal of the foamed area exhibited a well-ordered crystalline phase underneath polymer residues. In grazing angle X-ray scattering from the foamed region, a sharp peak from polyurethane crystallites was found on the shoulder of the amorphous peak; this reflection did not appear in the scans for unfoamed solid polymer areas. It is suggested that a greater number of these crystallites results in higher bond strength. A bond failure model was proposed in which fracture takes place along the non-connected regions, with cohesive failure in the foamed areas.