The combined atomic and molecular (CAM) ionisation with a liquid sampling-atmospheric pressure glow discharge (LS-APGD) has been explored in a wide variety of mass spectrometric techniques, proving its versatility beyond doubt. However, per – and polyfluoroalkyl substances (PFAS) have not yet been included in the scope of analysis. PFAS are anthropogenic compounds of emerging concern. Routine analysis of PFAS includes a few dozen of compounds from the more than 12000 registered ones, while the remaining cannot be included in the analysis due to ionisation challenges. In this study we used CAM – LS-APGD to analyse several different PFAS, both that can be done routinely, and cannot. Results show that not only the analysis of routine PFAS is possible, but CAM – LS-APGD shows promising results to analyse neutral, semi-volatile PFAS as well as perfluoroalkanes, although optimisation is necessary to achieve higher intensity peaks. Data also suggest that matrix can influence the signal intensity, which needs to be taken account in the data analysis process.