Extreme climate events—such as hurricanes, droughts, extreme precipitation, and wildfires—have the potential to alter watershed processes and stream response. Yet due to the destructive and hazardous nature and unpredictability of such events, capturing their hydrochemical signal is challenging. A 5‐year postwildfire study of stream chemistry in the Fourmile Creek watershed, Colorado Front Range, USA, focused on high‐frequency storm sampling. During the study, the watershed was impacted by three additional extreme climate events—drought and two periods of extreme rainfall totals. These events altered concentration‐discharge relationships in ways that elucidate how hydrologic flow paths and source material availability affect stream water chemistry. Reduced infiltration after wildfire led to overland flow during thunderstorms, which conveyed ash and soil into streams. This resulted in elevated stream concentrations of constituents elevated in ash—Ca, K, Mg, alkalinity, and dissolved organic carbon—along with sediment and nitrate. Subsurface flow paths were bypassed, leading to low concentrations of Na and SiO₂, which are bedrock derived and not elevated in ash. During drought conditions, when stream discharge was <20% of average, concentrations of sediment, dissolved organic carbon, and Ca fell below average concentrations, but SiO₂ did not. Extreme rainfall totals saturated the subsurface and led to prolonged elevated stream discharge. Concentration‐discharge relationships for bedrock‐derived constituents, such as Ca and SiO₂, were altered in that time period, while those for dissolved organic carbon were not. Previous disturbances, including historical mining, also affect stream chemistry, and water‐quality impairment can be exacerbated by extreme climate events.