The porous near‐surface layer of the Earth's crust – the critical zone – constitutes a vital reservoir of water for ecosystems, provides baseflow to streams, guides recharge to deep aquifers, filters contaminants from groundwater, and regulates the long‐term evolution of landscapes. Recent work suggests that the controls on regolith thickness include climate, tectonics, lithology, and vegetation. However, the relative paucity of observations of regolith structure and properties at landscape scales means that theoretical models of critical zone structure are incompletely tested. Here we present seismic refraction and electrical resistivity surveys that thoroughly characterize subsurface structure in a small catchment in the Santa Catalina Mountains, Arizona, USA, where slope‐aspect effects on regolith structure are expected based on differences in vegetation. Our results show a stark contrast in physical properties and inferred regolith thickness on opposing slopes, but in the opposite sense of that expected from environmental models and observed vegetation patterns. Although vegetation (as expressed by normalized difference vegetation index [NDVI]) is denser on the north‐facing slope, regolith on the south‐facing slope is four times thicker (as indicated by lower seismic velocities and resistivities). This contrast cannot be explained by variations in topographic stress or conventional hillslope morphology models. Instead, regolith thickness appears to be controlled by metamorphic foliation: regolith is thicker where foliation dips into the topography, and thinner where foliation is nearly parallel to the surface. We hypothesize that, in this catchment, hydraulic conductivity and infiltration capacity control weathering: infiltration is hindered and regolith is thin where foliation is parallel to the surface topography, whereas water infiltrates deeper and regolith is thicker where foliation intersects topography at a substantial angle. These results suggest that bedrock foliation, and perhaps by extension sedimentary layering, can control regolith thickness and must be accounted for in models of critical zone development. © 2020 John Wiley & Sons, Ltd.