Dhaka, the capital city, which is the nerve center of Bangladesh, is crisscrossed by six different rivers. A network of peripheral rivers connects the city and functions as a natural drainage system for a massive amount of wastewater and sewage by the increased number of inhabitants impacting the overall environmental soundness and human health. This study intended to identify and characterize the outfalls along the peripheral rivers of Dhaka city with the assessment of different pollution indices such as comprehensive pollution index (CPI), organic pollution index (OPI), and ecological risk indices (ERI). The study evaluated the status of the pollution in the aquatic system in terms of ambient water quality parameters along the peripheral rivers due to discharge from outfalls with a particular focus on waste load contribution. Among the identified outfalls, the majority are industrial discharge (60%), and some are originated from municipal (30%), or domestic sewers (10%). Water quality parameters such as suspended solids (SS), 5-day biochemical oxygen demand (BOD5), and Ammoniacal Nitrogen (NH3-N) for most of the peripheral rivers deviated by as much as 40–50% from industrial discharge standards by the environment conservation rules, Bangladesh, 1997. Based on the CPI, the rivers Buriganga, Dhaleshwari, and Turag could be termed as severely polluted (CPI > 2.0), while the OPI indicated heavy organic pollutant (OPI > 4) contamination in the Dhaleshwari and Buriganga rivers. The associated pollution indices demonstrate a trend for each subsequent peripheral river with significant pollution toward the downstream areas. The demonstrated waste loading map from the outfalls identified sources of significant environmental contaminants in different rivers leading to subsequent ecological risks. The study outcomes emphasize the necessity of systematic investigation and monitoring while controlling the point and non-point urban pollution sources discharging into the peripheral rivers of Dhaka city.