Water temperature is an important control on processes in aquatic systems and particularly for freshwater fish, affecting growth, survival and demographic characteristics. In recognition of this importance, the Scottish Government has prioritised developing a robust national river temperature monitoring network. Advances in geographical information systems, spatial statistics and field data loggers make large-scale river temperature monitoring increasingly possible. However, duplication of environmental and thermal characteristics among monitoring sites means many networks have lower than expected statistical power. This paper describes a novel methodology for network design, illustrated by the development of the Scotland River Temperature Monitoring Network. A literature review identified processes controlling stream temperature and associated landscape controls. Metrics indicative of these landscape controls were calculated for points every 500 m along the river network. From these points, sites were chosen to cover the full range of observed environmental gradients and combinations of controlling variables. The resulting network contains sites with unique characteristics covering the range of relevant environmental characteristics observed in Scottish salmon rivers. The network will thus have minimal redundancy, often not seen in large networks, and high statistical power to separate the relative importance of predictor variables thereby allowing large-scale water temperature predictions.