AbstractThis study investigates the possible correspondence between catchment structure, as represented by perceptual hydrological models developed from fieldwork investigations, and mathematical model structures, selected on the basis of reproducing observed catchment hydrographs. Three Luxembourgish headwater catchments are considered, where previous fieldwork suggested distinct flow‐generating mechanisms and hydrological dynamics. A set of lumped conceptual model structures are hypothesized and implemented using the SUPERFLEX framework. Following parameter calibration, the model performance is examined in terms of predictive accuracy, quantification of uncertainty, and the ability to reproduce the flow–duration curve signature. Our key research question is whether differences in the performance of the conceptual model structures can be interpreted based on the dominant catchment processes suggested from fieldwork investigations. For example, we propose that the permeable bedrock and the presence of multiple aquifers in the Huewelerbach catchment may explain the superior performance of model structures with storage elements connected in parallel. Conversely, model structures with serial connections perform better in the Weierbach and Wollefsbach catchments, which are characterized by impermeable bedrock and dominated by lateral flow. The presence of threshold dynamics in the Weierbach and Wollefsbach catchments may favour nonlinear models, while the smoother dynamics of the larger Huewelerbach catchment were suitably reproduced by linear models. It is also shown how hydrologically distinct processes can be effectively described by the same mathematical model components. Major research questions are reviewed, including the correspondence between hydrological processes at different levels of scale and how best to synthesize the experimentalist's and modeller's perspectives. Copyright © 2013 John Wiley & Sons, Ltd.