Stream temperature, an important measure of ecosystem health, is expected to be altered by future changes in climate and land use, potentially leading to shifts in habitat distribution for aquatic organisms dependent on particular temperature regimes. To assess the sensitivity of stream temperature to change in a region where such a shift has the potential to occur, we examine the variability of and controls on the direct relationship between air and water temperature across the state of Pennsylvania. We characterized the relationship between air and stream temperature via linear and nonlinear regression for 57 sites across Pennsylvania at daily and weekly timescales. Model fit (r2) improved for 92% (daily) and 65% (weekly) of sites for nonlinear versus linear relationships. Fit for weekly versus daily regression analysis improved by 0·08 for linear and 0·06 for nonlinear regression relationships. To investigate the mechanisms controlling stream temperature sensitivity to environmental change, we define ‘thermal sensitivity’ as the sensitivity of stream temperature of a given site to change in air temperature, quantified as the slope of the regression line between air and stream temperature. Air temperature accounted for 60–95% of the daily variation in stream temperature for sites at or above a Strahler stream order (SO) of 3, with thermal sensitivities ranging from low (0·02) to high (0·93). The sensitivity of stream temperature to air temperature is primarily controlled by stream size (SO) and baseflow contribution. Together, SO and baseflow index explained 43% of the variance in thermal sensitivity across the state, and 59% within the Susquehanna River Basin. In small streams, baseflow contribution was the major determinant of thermal sensitivity, with increasing baseflow contributions resulting in decreasing sensitivity values. In large streams, thermal sensitivity increased with stream size, as a function of accumulated heat throughout the stream network. Copyright © 2011 John Wiley & Sons, Ltd.