Field and mesocosm studies repeatedly show that higher tier processes reduce the predictive accuracy of toxicity evaluation and thus their value for pesticide risk assessment. Therefore, understanding the influence of ecological complexity on toxicant effects is crucial to improve realism of aquatic risk assessment. Here we investigate the influence of repeated exposure to ecologically realistic concentrations of esfenvalerate on the two similarly sensitive species Daphnia magna and Culex pipiens in a food limited and highly competitive environment. We show that significant perturbations in population development are only present at 100 ng/L (close to the EC50). In contrast, interspecific competition between species is already reduced at 0.1 ng/L (≤ 3 orders of magnitude below the acute lethal EC50). We conclude that extremely low, environmentally relevant concentrations can disrupt species interactions. This toxicant mediated alteration of competitive balances in ecological communities may be the underlying mechanism for shifts in species distribution at ultra-low pesticide concentrations. A realistic risk assessment should therefore consider these processes in order to predict potential pesticide effects on the structure of communities.