There is a need to identify measurable characteristics of stream channel morphology that vary predictably throughout stream networks and that influence patterns of hyporheic exchange flow in mountain streams. In this paper we characterize stream longitudinal profiles according to channel unit spacing and the concavity of the water surface profile. We demonstrate that: (1) the spacing between zones of upwelling and downwelling in the beds of mountain streams is closely related to channel unit spacing; (2) the magnitude of the vertical hydraulic gradients (VHGs) driving hyporheic exchange flow increase with increasing water surface concavity, measured at specific points along the longitudinal profile; (3) channel unit spacing and water surface concavity are useful metrics for predicting how patterns in hyporheic exchange vary amongst headwater and mid-order streams. We use regression models to describe changes in channel unit spacing and concavity in longitudinal profiles for 12 randomly selected stream reaches spanning 62 km2 in the H.J. Andrews Experimental Forest in Oregon. Channel unit spacing increased significantly, whereas average water surface concavity (AWSC) decreased significantly with increasing basin area. Piezometer transects installed longitudinally in a subset of stream reaches were used to measure VHG in the hyporheic zone, and to determine the location of upwelling and downwelling zones. Predictions for median pool length and median distance between steps in piezometer reaches bracketed the median distance separating zones of upwelling in the stream bed. VHG in individual piezometers increased with increasing water surface concavity at individual points in the longitudinal profile along piezometer transects. Absolute values of VHG, averaged throughout piezometer transects, increased with increasing AWSC, indicating increased potential for hyporheic exchange flow. These findings suggest that average hyporheic flow path lengths increase—and the potential for hyporheic exchange flow in stream reaches decreases—along the continuum from headwater to mid-order mountain streams. Copyright © 2005 John Wiley & Sons, Ltd.