Exterior and interior automotive applications of TPO (thermoplastic polyolefin) resins, which are, often, composed of a paint coating over an injection-molded TPO, have increased interest in the surface chemistry and physics of TPOs. Specifically, the interface system composed of base-coat paint/adhesion promoter/TPO is of primary importance in controlling the paint adhesion to the TPO. The major, active component in the adhesion promoter is a chlorinated polypropylene (CPO). A theoretical model based on phase thermodynamics and diffusion kinetics resulted in a prediction that the TPO/CPO interface should have a lower bound thickness of about 11 nm and an upper bound of about 400 nm. A battery of experimental strategies to characterize this interface system was discussed. Techniques used were transmission electron microscopy (TEM). atomic force microscopy (AEM) and scanning transmission X-ray microscopy (STXM). The near-surface morphology of both unpainted and painted, injection molded TPO plaques exhibited ethylene-propylene rubber particles close to the surface, i.e. within the first 0.1-0.8 micrometer of the TPO surface, and no "overlayer" of transcrystalline polypropylene at the surface of the TPO. Each of these microscopic methods shaved that the adhesion promoter/TPO interface was very sharp. The thickness of this interface was measured with respect to the interdiffusion of the CPO and TPO by STXM. The STXM measurements yielded an apparent interface thickness between the adhesion promoter and TPO of 340 +/- 80 nm. This was in good agreement with the theoretical predictions.