Large‐scale cross‐site scientific synthesis on low‐flow storage‐discharge relation can promote developing transferable hypotheses on the interactions amongst critical zone attributes, and on how such interactions affect catchments' water vulnerabilities. This study leverages cross‐site empirical and theoretical analyses and develops a similarity index, based on the interactions amongst critical zone attributes, to determine the poorly‐studied influence of upland hillslope groundwater subsidy on storage‐discharge relation. We show that an increase in the relative extent of upland hillslope groundwater subsidy to low‐flow discharge, occurring through deep slow low‐moving (e.g., bedrock) storage‐unit, leads to 1) an increase in the nonlinearity of low‐flow discharge sensitivity to storage (β1), and 2) an increase in the convexity of low‐flow storage‐discharge relation. Our findings also raise new hypotheses on the applicability of Boussinesq‐based hydraulic groundwater theory at low‐flow condition. Empirical results show that in a portion of our study catchments, particularly in those with a relatively small extent of upland hillslope groundwater subsidy, the theory’s proposed range of nonlinearity sufficiently explains the nonlinearity of low‐flow storage‐discharge relation. However, in catchments with a strong influence of upland hillslope groundwater subsidy through deep slow‐moving storage‐unit the current state of hydraulic groundwater theory, using one single (non) linear representative storage‐unit, may not be sufficient to explain the large nonlinearity and convexity of low‐flow storage‐discharge relation (or the long tail of late‐recession). As β1 informs the low‐flow vulnerability of catchments, this study’s findings deepen and generalize our understanding of where low‐flow discharge is vulnerable to storage’s change.