The African Copperbelt is a site of intense artisanal and industrial mining and refining of copper and cobalt. We aimed to investigate factors that are possibly associated with erectile dysfunction (ED) in metal miners in the former Katanga province of the Democratic Republic of the Congo. In a cross-sectional study of 138 miners and 139 controls (bakers), we administered questionnaires to obtain sociodemographic and occupational data and to assess male sexual function (International Index of Erectile Function [IIEF]) and marital relation quality (Revised Dyadic Adjustment Scale). Furthermore, we measured trace metals in blood and urine, as well as testosterone and thyroid hormones in serum. Outcomes included the prevalence of questionnaire-derived ED and the relation of ED with individual characteristics, serum testosterone, and environmental factors. Miners were on average 4years older than bakers (mean ± SD, 37.5 ± 6.9 vs 33.3 ± 5.7 years). Miners had significantly lower scores than bakers on the IIEF (median [IQR], 66 [49-73] vs 73 [66-74]) and the 3 domains of the Revised Dyadic Adjustment Scale (consensus, satisfaction, cohesion). Free testosterone was significantly lower in miners than bakers (ng/dL; 8.11 [6.90-10.10] vs 10.52 [8.83-12.58]; P ˂ .001). In miners, sex hormone-binding globulin correlated positively with blood Pb and urinary Cd. In a multivariable analysis, mild to moderate ED or moderate ED (IIEF-erectile function score ≤18) was significantly associated with having a mining-related job (adjusted odds ratio [aOR], 2.6; 95% CI, 1.3-5.3), work seniority ˃5years (aOR, 2.3; 95% CI, 1.1-4.6), alcohol consumption (aOR, 2.8; 95% CI, 1.2-6.7), and aphrodisiacs use (aOR, 4.2; 95% CI, 2.2-8.0). Mediation analysis showed that marital relationship partially mediated the relation between work seniority >5years in mining and ED. The high prevalence of ED found in artisanal mine workers indicates that work-related factors should be considered as possibly contributing, directly or indirectly, to sexual dysfunction in men. Strengths include being the first epidemiologic study documenting ED with validated questionnaires and its possible determinants, including exposure to toxic metals, among young artisanal miners vs a suitable control group. Limitations are the cross-sectional design with convenience sampling and absence of objective confirmation of ED. As compared with controls, miners reported poorer sexual function and lower quality of their marital relationship, and they had lower free testosterone levels, which may be due to their high exposure to trace metals.