Payments for Ecosystem Services (PES) schemes are an increasingly popular form of catchment management for improving surface water and groundwater quality. In these schemes, downstream water users who are impacted by agricultural diffuse pollution incentivise upstream farmers to adopt better practices. However, this type of scheme will not be successful in all situations, in part, due to a lack of potential for agriculture to improve the suuply of good water quality and/or a lack in demand from downstream users for good water quality. As such, this study aims to present a flexible approach to mapping the potential for PES schemes to improve water quality in agricultural catchments. The approach is based on multi-criteria analysis, with supply and demand as key criteria. It uses expert judgement or current guidance on PES to select supply and demand sub-criteria, expert judgement to weight all criteria through pairwise comparisons and readily available, national datasets to indicate criteria. Once indicator data are normalized, it combines them in a weighted sums analysis and presents results spatially at the national scale, all within a geographical information system. The approach can easily be applied to the country or region of interest by using locally relevant criteria, expert judgement and data. For example, when applied to the situation for river waterbodies in England, supply sub-criteria were the contribution of agriculture to loads of the major pollutants (nitrogen, phosphorus and sediments) and demand sub-criteria were the different downstream water users present (water companies and, tourist and local recreational users). Experts assigned equal weight to supply and demand criteria and the highest weights to sediments and water companies for sub-criteria, respectively. When national scale datasets to indicate these criteria were combined in a weighted sums analysis, it was possible to identify areas of high potential for PES. This would hopefully motivate more detailed research at the individual catchment level into the constraints in linking supply and demand. Three case-study schemes were also examined to show how some of these constraints are being identified and overcome. As such, the approach forms the first tier in a two-tier framework for establishing PES schemes to improve water quality in agricultural catchments. [Abstract copyright: Copyright © 2021. Published by Elsevier Ltd.]