Complexity of contaminants exposure needs to be taking in account for an appropriate evaluation of risks related to mixtures of pesticides released in the ecosystems. Toxicity assessment of such mixtures can be made through a variety of toxicity tests reflecting different level of biological complexity. This paper reviews the recent developments of passive sampling techniques for polar compounds, especially POCIS and Chemcatcher®, and the progresses permitted by the coupled use of such passive samplers and ecotoxicology testing as well as their limitations. Case studies combining passive sampling devices (PSD) extracts and toxicity assessment toward microorganisms at different biological scales from single organisms to communities level, respectively aiming i) at characterizing the "toxic potential" of waters using short-term tests, and ii) at performing microcosm experiments with increased environmental realism in the toxicant exposure in term of cocktail composition and concentration are then presented. Finally perspectives and limitations of such approaches for future applications in the area of environmental risk assessment are discussed.