To inform the design and implementation of land-use policies that consider the variety of goods and services people derive from ecosystems, it is essential to understand spatial patterns of individual services, how multiple services relate to each other, and how these relationships vary across spatial scales and localities. Despite the importance of freshwater as a determinant of regional economic and human demographic patterns, there are surprisingly few studies that map the provision of a range of services associated with the quality of the aquatic environment. Here we examine relationships between indicators of riverine water and associated habitat quality, freshwater biodiversity, three terrestrial ecosystem services, and terrestrial biodiversity across England and Wales. The results indicate strong associations between our indicators of freshwater services. However, a comparison of these indicators of freshwater services with other ecosystem services (carbon storage, agricultural production, recreation) and biodiversity of species of conservation concern in the surrounding terrestrial landscape shows no clear relationships. While there are potential policy “win–wins” for the protection of multiple services shown by associations between indicators of freshwater services and carbon storage in upland areas of Britain, the other ecosystem services showed either negative or no relationships with the indicators of freshwater services. We also consider the influence that spatial scale has on these relationships using River Basin Districts. Our results indicate that relationships between indicators of services can change dramatically depending on the societal pressures and other regional conditions. Thus, the delivery of multiple ecosystem services requires the development of regional strategies, or of national strategies that take account of regional variation.