Polypropylene (PP) is used in many automotive applications where good paint adhesion is of primary importance. PP is widely known for its low surface energy which impacts negatively on its adhesion strength. PP surfaces were modified using a new industrial surface-treatment process known as the Accelerated Thermo-molecular adhesion Process (ATmaP). ATmaP grafts functional groups to the polymer surface derived from an atomised and vapourised nitrogen-containing coupling agent. The surface properties and adhesion performance of PP samples treated using the ATmaP process and two different flame processes were compared using XPS, time-of-flight secondary ion mass spectrometry (ToF-SIMS) and mechanical testing (pull-up tests). The latter showed that ATmaP improved adhesion strength significantly in comparison with conventional flame treatments. XPS showed an increase in oxygen and nitrogen concentration on the surface of ATmaP-treated samples compared with untreated and flame-treated samples. Principal components analysis (PCA) of the ToF-SIMS data revealed the major phenomena occurring during the surface treatment of PP samples. Early stage events, including the chain scission of the PP backbone chain and the subsequent reaction of these chains with the surrounding air, are captured by the first principal component (PC1). The increase in the concentration of NO surface functional groups resulting from ATmaP treatment is captured by the second principal component (PC2). Copyright © 2008 John Wiley & Sons, Ltd.