South Africa mainly relies on Eskom's coal-fired power plants for electricity generation. However, the use of coal causes several adverse environmental impacts, including the release of selenium into the hydrosphere. Selenium is an essential nutrient for humans, animals, and microbes, but excess selenium is toxic. This paper describes the determination of total dissolved selenium in wastewater from selected coal-fired power plants and river waters near coal-fired power plants in South Africa. A sensitive and robust inductively coupled plasma mass spectrometry (ICP-MS) method for determining total dissolved selenium in wastewater and river water was developed using a certified reference material (NIST SRM 1640a Trace Elements in Natural Water). The results agreed with the certified values, with percentage recoveries ranging from 92–96%. The method detection limit was 0.13 µg/L. Total Se concentrations in wastewater samples from Kriel and Lethabo Power Stations ranged between 4.86 and 8.53 µg/L, and in river water samples from the Olifants and Wilge Rivers, the concentrations ranged from 2.63–8.20 µg/L. These results indicate that the Se levels in the wastewater are too low to pose a health hazard to humans and livestock but pose an environmental threat to aquatic life. The low concentrations in the river samples also show that there may be slight Se pollution (regarding aquatic life) from the selected coal-fired power plants in South Africa. There may be slight Se pollution (with regards to aquatic life) from Duvha and Kendal Power Stations because an increase from 2–8 µg/L was observed in river water samples collected near these selected coal-fired power plants.