Many freshwater ecological studies focused on the effects of environmental stressors induced by anthropogenic activities such as land use or alteration of hydromorphology and physico-chemistry conditions. While it is recognized as a potential major driver of ecological alteration, ecotoxicological stress is yet rarely explicitly considered. By combining ecological monitoring and field ecotoxicological approaches, the purpose of this research is to focus on the origin and levels of bioavailable contamination as well as toxicity in freshwater ecosystems taking into account various stream typologies and unraveling the relative impacts of other stressors on these two variables. Datasets of active biomonitoring at the French national scale were established, with 333 sites being investigated from 2009 to 2018. Bioavailable contamination (metallic and persistent organic substances) in freshwater ecosystems was assessed by bioaccumulation measurement in caged Gammarids. Stream toxicity was based on mortality and feeding activity of exposed organisms. For each site, integrated indicators of contamination and toxicity were computed with weighting chemical and biological measurements by national reference values. The link between environmental stressors and ecotoxicological indicators was modeled via Structural Equation Modeling. The model was adjusted according to the source of pollution and is reliable with the consideration of multi-scale and multi-stressor concepts. It enables to understand the role of driving forces (land use, hydromorphology, etc.) and their impact on the two outputs (contamination and toxicity). Its application improves the understanding of contamination and toxicity levels. It can also provide a prediction of risks of contamination and/or toxicity in aquatic environments.