Perfluoroalkyl acids (PFAAs) have emerged as global concerning contaminants because of their persistence, bioaccumulation, and toxicological effects. The transport and fate of PFAAs on dimension of plain river networks (PRNs) are difficult to model due to the unique regional characteristics (i.e., undirectional flows, low slope, complicated structure and connectivity) and the lack of data on PFAAs concentrations and compositions. A typical PRN (Taihu Basin, China) was selected to elucidate the spatial patterns of PFAAs in multi-matrices, including colloidal phase, soluble phase, suspended particles, and sediment. PFAAs were ubiquitously detected in plain rivers with total concentrations of 18.48–1220 ng/L in colloids, 139.07–721.37 ng/L in soluble phase, 97.69–2247 ng/g dw in suspended particles, and <72.04–178.12 ng/g dw in sediment. PFAAs were more likely to transport via dissolved phase and accumulate into sediment. Colloids carried 45.46–62.59% of ∑PFAAs in overlying water, while suspended particles contained <36.63% of ∑PFAAs, suggesting the important role of colloids in preloading PFAAs. Moreover, PFAAs variability was correlated with indicators of the structure and connectivity of river network by gray relational analysis. The mean gray relational degrees can be sorted as edge-node ratio (0.7609) > network connectivity (0.7191) > river density (0.7012) > water surface ratio (0.6887) > river development coefficient (0.6504) > functional connectivity (0.4780). These results suggested that the effects of catchment characteristics should be taken into account in understanding PFAAs fate in the PRNs.