In this narrative account based on a keynote presentation on exposure biomonitoring of metals in low- and middle-income countries (LMIC), we first briefly address practical issues that have arisen from our experience during the conduct of various surveys in LMIC. These have included the statistical handling of multiple pollutants in the same subject, the problem of correctly adjusting for urinary flow in spot samples of urine, and the possible external contamination of samples when doing field surveys in challenging environments. We then review and present selected results from surveys conducted in the mining area of Katanga in the Democratic Republic of Congo (DR Congo), where we documented high urinary levels of cobalt and other trace metals (arsenic, uranium) in people living close (<3 km) to mining or smelting operations (Banza et al., 2009). Consumption of contaminated foodstuffs (maize, legumes, fish) and, especially among children, dust ingestion proved to be the main sources of exposure to cobalt (Cheyns et al., 2014). Urinary biomonitoring studies among artisanal workers involved in mining cobalt, craftsmen working malachite, and workers processing gold ore revealed high to extremely high values of cobalt (largely exceeding the Biological Exposure Index of 15 μg/L), as well as other trace metals such as uranium, manganese, lead or mercury, depending on the type of jobs. This abundant biomonitoring data has been valuable to argue for improved enforcement of legislation to protect workers and citizens against the hazards posed by the mining activities in the area. Epidemiological studies have been undertaken and are ongoing to assess the human health impact of this pollution.