Urban stormwater runoff is an important source of pollution in receiving water bodies, mainly in cities in development. However, strategies to deal with the impacts caused by the runoff discharges, such as implementing a sustainable urban drainage system (SUDS) with optimized management, need information usually obtained through monitoring studies. Brasília is a city that has one of the highest urban growth rates in Brazil, with significant impacts on urban water resources, including diffuse pollution, generated by new unregulated urban developments that initially start being built with precarious sanitation infrastructure. The Vicente Pires (VP) watershed is highly urbanized and comprises two areas that have been intensively occupied more recently, at a fast pace, and do not have yet basic sanitation systems fully implemented. Stormwater quality at the outlet of the VP watershed was analyzed by monitoring the rainfall, runoff flows, and pollutant concentration. Event Mean Concentration (EMC) and first-flush (FF) phenomenon were calculated, and hydrologic characteristics were compared for different events through correlation analysis. During dry periods the flow varied between 0.5 and 1.29 m3/s, while in flood periods the maximum value was 72.17 m3/s, forming floods with great volume. Nitrate during dry periods stands out with its high concentration; the maximum was 1.49 mg/L, while the maximum concentration during the flood events was 0.43 mg/L, probably due to dilution. Ammonia results showed very low values, probably because nitrification is occurring up to the collection point. The EMC values of solids in flood events were higher and can be attributed to river bed scour along the VP watershed. The EMC SS values for the VP watershed are also similar to areas in the initial stages of building development. The EMC values in the dry season indicate strong correlations between some water quality parameters such as NH+3-N and SS, TS and NO−3-N; NO−3-N, and COD. These correlations indicate that these pollutants are probably being generated by the same source, probably sewage discharges. During flood events, the correlation between pollutant loads and peak flow can be associated with the scouring during surface washing off, because greater concentrations of solids and organic matter occur in events with greater flow rates. For the first 30% of the initial runoff volume, about 29% of SS, 38% of NH+3-N, and 35% of reactive P were carried during flood events. It was verified that large values of maximum or mean rainfall intensity are related to the occurrence of First Flush (FF) for most pollutants. Antecedent dry days (ADD) did not influence build-up processes in this watershed; however, they are related to FF occurrence. Data indicate that the sewage and stormwater collection networks were being installed caused a high impact on observed water quality, with high concentrations of solids during flood events. On the other hand, the wastewater collection after the sewer network installation led to a decrease in COD concentrations over time. For sustainable management of diffuse pollution, the adoption of distributed SUDS to enhance runoff volume reduction is a recommended solution for the case.