Changes in regional climate in the Rocky Mountains over the next 100 years are expected to have significant effects on biogeochemical cycles and hydrological processes. In particular, decreased discharge and lower stream depth during summer when ultraviolet radiation (UVR) is the highest combined with greater photo-oxidation of dissolved organic materials (DOM) will significantly increase exposure of benthic communities to UVR. Communities in many Rocky Mountain streams are simultaneously exposed to elevated metals from abandoned mines, the toxicity and bioavailability of which are also determined by DOM. We integrated field surveys of 19 streams (21 sites) along a gradient of metal contamination with microcosm and field experiments conducted in Colorado, USA, and New Zealand to investigate the influence of DOM on bioavailability of heavy metals and exposure of benthic communities to UVR. Spatial and seasonal variation in DOM were closely related to stream discharge and significantly influenced heavy metal uptake in benthic organisms. Qualitative and quantitative changes in DOM resulting from exposure to sunlight increased UV-B (290–320 nm) penetration and toxicity of heavy metals. Results of microcosm experiments showed that benthic communities from a metal-polluted stream were tolerant of metals, but were more sensitive to UV-B than communities from a reference stream. We speculate that the greater sensitivity of these communities to UV-B resulted from costs associated with metal tolerance. Exclusion of UVR from 12 separate Colorado streams and from outdoor stream microcosms in New Zealand increased the abundance of benthic organisms (mayflies, stoneflies, and caddisflies) by 18% and 54%, respectively. Our findings demonstrate the importance of considering changes in regional climate and UV-B exposure when assessing the effects of local anthropogenic stressors.