Watersheds continue to be urbanized across different regions of the United States, increasing the number of impaired waterbodies due to urban stormwater. Using machine learning techniques, this study examined how stormwater quality and watershed characteristics are related at a national scale and compared stormwater quality across watersheds in diverse climates. We analyzed a selection of data from the National Stormwater Quality Database (NSQD) comprising 1,881 stormwater samples taken from 182 watersheds in 26 metropolitan areas in the United States between 1992 and 2003. Using an ensemble clustering algorithm, the stormwater quality in these samples was classified into "stormwater signatures," defined as distinct combinations of 9 contaminants including metals (Pb, Zn, Cu), particulates (TSS, TDS), and nutrients (BOD, TP, TKN, NOx). Next, multinomial logistic regression was applied to the NSQD data now classified by signature and combined with climate, weather, land use, and imperviousness data obtained from multiple sources. The results yielded 5 stormwater signatures with distinct aquatic toxicity implications and relationships to climate, weather, land use, and imperviousness: Signature 1 ("Ecotoxic and Eutrophic"), defined by high median concentrations of contaminants, likely represents the first flush in moderate-to-high imperviousness watersheds; Signature 2 ("Reduced Nitrates") represents a wet season signature, particularly for dry climates; Signature 3 ("Potentially Eutrophic") represents the first flush in low imperviousness watersheds; Signature 4 ("Elevated Particulates and Metals") represents a wet season signature, particularly on warmer days; finally, Signature 5 ("Most Dilute") is primarily a regional signature associated with the warm, wet climate of the southeastern US. This study serves as a proof-of-concept demonstrating how machine learning techniques can be used to identify patterns in high-dimensional and highly variable data. Applied to stormwater quality, these techniques identify major patterns in stormwater quality across the United States using a stormwater signature approach, which examines how contaminants co-occur and under what climate, weather, land use, and impervious conditions. The findings point to dominant processes driving stormwater generation and inform watershed monitoring, green infrastructure planning, stormwater quality under climate change, and opportunities for public engagement.