Abstract. The spatial and temporal variation of concentration-discharge (C-Q) relationships inform solute and particulate export processes. Previous studies have shown that the extent to which baseflow contributes to streamflow can affect C-Q relationships in some catchments. However, these patterns have not yet been investigated across large spatial scales. To address this, the study aims to assess how baseflow contributions, as defined by the median catchment baseflow index (BFI_m), influence C-Q slopes across 157 catchments in Australia spanning five climate zones. This study focuses on six water quality variables: electrical conductivity (EC), total phosphorus (TP), soluble reactive phosphorus (SRP), total suspended solids (TSS), nitrate–nitrite (NOx) and total nitrogen (TN). The impact of baseflow contribution is explored with a novel Bayesian hierarchical model. We found that BFI_m has a strong impact on C-Q slopes. C-Q slopes are largely positive for nutrient species (NOx, TN, SRP and TP) and are steeper in catchments with higher BFI_m across all climate zones (for TN, SRP and TP). On the other hand, we also found a generally higher variation in instantaneous BFI for catchments with high BFI_m. Thus, the steeper C-Q slopes found in catchments with high BFI_m may be a result of a larger variation in water sources and flow pathways between low (baseflow-dominated) and high (quickflow-dominated) flow conditions. In contrast, catchments with low BFI_m may have more homogeneous flow pathways at both low and high flows, resulting in less variable concentrations and thus a flatter C-Q slope. Our model can explain over half of the observed variability in concentration of TSS, EC and P species across all catchments (93 % for EC, 63 % for TP, 63 % for SRP, and 60 % for TSS), while being able to predict C-Q slopes across space by BFI_m. This indicates that our parsimonious model has potential for predicting the C-Q slopes for catchments in different climate zones, and thus improving the predictive capacity for water quality across Australia.