Bioaccumulated toxic metals in tolerant biomonitors are indicators of metal bioavailability and can be calibrated against metal‐specific responses in sensitive species, thus creating a tool for defining dose–response for metals in a field setting. Dose–response curves that define metal toxicity in natural waters are rare. Demonstrating cause and effect under field conditions and integrated chemical measures of metal bioavailability from food and water is problematic. The total bioaccumulated metal concentration in any organism that is a net accumulator of the metal is informative about metal bioavailability summed across exposure routes. However, there is typically no one universal metal concentration that is indicative of toxicity, especially across species, largely because of interspecies differences in detoxification. Stressed organisms are also only present across a narrow range in the dose–response curve, limiting the use of singles species as both biomonitors and bioindicator of stress. Herein we show, in 3 field settings, that bioaccumulated Cu concentrations in a metal‐tolerant, riverine biomonitor (species of the caddisfly genus Hydropsyche spp.) can be calibrated against metal‐specific ecological responses across very wide ranges of contamination. Using the calibrated dose–response, we show that reduced abundance of species and individuals from particularly sensitive mayfly families (heptageniid mayflies) is more than 2‐fold more sensitive to bioavailable Cu than other traditional measures of stress like EPT or total number of benthic macroinvertebrate species. We propose that this field dose‐response curve be tested more widely for general application, and that calibrations against other stress responses be developed for biomonitors from lakes, estuaries, and coastal marine ecosystems.