Polyolefins are used over a wide range of industries due to their low cost and adaptable mechanical properties. However, their low surface energy makes fabricating composites and applying coatings challenging. Therefore, various surface treatments have been utilized to enhance their adhesion properties. In this paper, the surface energies of various thermoplastic polyolefins (TPO) have been measured via Inverse Gas Chromatography (IGC). These surface energy values were correlated to mechanical adhesion testing of the painted polyolefins. The adhesive integrity of the painted TPO was determined by applying a comprehensive-shear load to the material. Higher surface energies measured by IGC lead to increased adhesion with the paint. The surface energies also correlate with TPO crystallinity, as determined by microhardness testing of the unpainted TPO.