Identification of the most sensitive hydrological regions to a changing climate is essential to target adaptive management strategies. This study presents a quantitative assessment of spatial patterns, inter‐annual variability and climatic sensitivity of the shape (form) and magnitude (size) of annual river/stream water temperature regimes across England and Wales. Classification of long‐term average (1989–2006) annual river (air) temperature regime dynamics at 88 (38) stations within England and Wales identified spatially differentiable regions. Emergent river temperature regions were used to structure detailed hydroclimatological analyses of a subset of 38 paired river and air temperature stations. The shape and magnitude of air and water temperature regimes were classified for individual station‐years; and a sensitivity index (SI, based on conditional probability) was used to quantify the strength of associations between river and air temperature regimes. The nature and strength of air–river temperature regime links differed between regions. River basin properties considered to be static over the timescale of the study were used to infer modification of air–river temperature links by basin hydrological processes. The strongest links were observed in regions where groundwater contributions to runoff (estimated by basin permeability) were smallest and water exposure time to the atmosphere (estimated by basin area) was greatest. These findings provide a new large‐scale perspective on the hydroclimatological controls driving river thermal dynamics and, thus, yield a scientific basis for informed management and regulatory decisions concerning river temperature within England and Wales. © 2013 The Authors. Hydrological Processes published by John Wiley & Sons, Ltd.