Strong dissimilar materials joints consisting of aluminum alloy and polyamide 66 (PA66) plates were produced by a new joining method: friction lap welding (FLW). To understand the key joining mechanism, special samples were made by evaporation of aluminum oxide onto PA66 plates to form an aluminum alloy/PA66 interface. X-ray photoelectron spectroscopy (XPS) was used for characterizing the resulting interfacial chemistry in these aluminum alloy/PA66 samples. Both the Al2p and C1s spectra of XPS confirmed the formation of AlOC bonds at the interface between PA66 and alumina coating. Approximately 23.6% of the Al atoms in the 0.8 nm alumina coating have contributed to the formation of AlOC bonds. The carbonyl group at the PA66 surface played an essential role in the formation of such an AlOC bond. The formation of AlOC bonds was proved to be a key factor for achieving good joint strengths in such metal/polymer joints, providing a direct understanding why aluminum alloys can be directly welded to PA66 plates with superior joint strength.