Extensive and long-term use of per- and polyfluoroalkyl substances (PFASs) has caused their widespread distribution in aquatic systems. A new diffusive gradients in thin-films (DGT) passive sampling method based on weak anion exchanger (WAX) binding layer is developed here for monitoring five perfluoroalkyl carboxylic acids (PFCAs), five perfluoroalkanesulfonic acids (PFSAs) and two PFASs (6:2 FTSA and GenX) in waters. Performance of WAX-DGTs was independent of environmental conditions, namely pH (3.03-8.96), ionic strength (1-500 mM), and DOM content (4-30 mg L-1). Diffusion coefficients (D) of the 12 PFASs in the diffusive gels were measured, 9 for the first time. Linear correlations between D and perfluoroalkyl chain lengths (CF2) were established to obtain D for congener chemicals with the similar functional group and structure. The binding capacity of the WAX-DGT sampler was at least 440 μg PFASs per sampler, sufficient for applications in waters across a wide range of conditions and PFASs concentrations. Successful applications of WAX based DGT samplers in a wastewater treatment plant (WWTP) and three rivers has demonstrated that DGT is a powerful tool for monitoring, surveillance and research of these 12 PFASs in aquatic systems, and can be extended to wider suites of PFs in future.