Pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) has been recognised as an effective technique to analyse car paint. This study was conducted to assess the combination of Py-GC-MS and chemometric techniques to classify car paint primer, the inner layer of car paint system. Fifty car paint primer samples from various manufacturers were analysed using Py-GC-MS, and data set of identified pyrolysis products was subjected to principal component analysis (PCA) and discriminant analysis (DA). The PCA rendered 16 principal components with 86.33% of the total variance. The DA was useful to classify the car paint primer samples according to their types (1k and 2k primer) with 100% correct classification in the test set for all three modes (standard, stepwise forward and stepwise backward). Three compounds, indolizine, 1,3-benzenedicarbonitrile and p-terphenyl, were the most significant compounds in discriminating the car paint primer samples.