Source apportionment of per- and polyfluoroalkyl substances (PFAS) in rivers is typically based on water concentrations, which cannot quantify PFAS loads or define geographical source areas. This study applied a river catchment-scale approach to identify PFAS source zones and assess the relative importance of industrial PFAS sources in the River Mersey, UK – a post-industrial, densely populated catchment with diverse PFAS sources. Synoptic sampling and PFAS river load analysis identified key sub-catchments and river stretches contributing the majority of PFAS. Notably, the highest PFAS concentrations did not always correspond to the greatest loads. Most PFOS (64 %), PFOA (49 %), 6:2FTS (46 %) and PFHxS (56 %) were exported from the Upper Mersey sub-catchment, despite higher concentrations in northern sub-catchments, emphasising the importance of load-based monitoring. Mass balance analysis of loads highlighted substantial inputs from specific river stretches, notably the Lower Irwell (Bolton to Manchester City Centre), River Tame (Marple Bridge to Stockport), and Upper Mersey (Stockport to Urmston). While PFAS loads generally scaled with catchment area, yield (load per unit area) analysis identified disproportionately high exports from small headwater catchments, notably the upper River Roch (PFOA, PFHpA and PFHxA) and Glaze Brook (PFBS). Industrial sources in these sub-catchments (a waste management facility and landfills, respectively) were confirmed using gadolinium anomaly analysis and consented discharge records. More widely, gadolinium data suggested industrial discharges may contribute to PFAS occurrence at 62 % of our sample sites throughout the catchment. These findings demonstrate that spatial analysis of PFAS loads, rather than concentrations alone, is critical for identifying PFAS source areas. We present a scalable monitoring framework for PFAS source apportionment applied at the river catchment-scale that can be used by environmental managers to target and prioritise PFAS source areas for detailed monitoring and remediation.