This study focused on assessing the extent of pollution in both flowing and non-flowing surface water within the Matjhabeng mining area of South Africa, with particular emphasis on the substantial impact of gold mine tailings. A comprehensive analysis of physical water-quality attributes, including potentially toxic elements (PTEs), and relevant pollution risk indices was undertaken. To comprehensively elucidate the potential risks to aquatic organisms and human health, a risk assessment framework predicated upon the source–pathway–receptor model was developed. Principal Component Analysis (PCA) was employed as a multivariate statistical tool to discern the potential origins of PTE contamination within the environment. The results substantiate pronounced pollution manifestations within the surface water milieu of the Matjhabeng mining area. Specifically, concentrations of critical PTEs, such as arsenic, cobalt, copper, iron, selenium, and zinc, exhibited transgressions of the regulatory thresholds stipulated by both the South African Department of Water Affairs and Forestry (DWAF) and the Canadian Council of the Ministers of the Environment (CCME). Additionally, concentrations of the aforementioned elements exceeded the stipulated DWAF guidelines for irrigation water usage. Pollution indices, encompassing the Single-Factor Pollution Index and the Nemerow Integrated Pollution Index, discerned moderate contamination stemming from As, while remarkably elevated pollution levels were identified for selenium. PCA elucidated 94.5% of the aggregate variance, revealing cobalt, copper, nickel, and zinc as coalescing within PC1, indicative of a common anthropogenic provenance that is conceivably linked to historical gold mine tailings. PC2 exhibited an aggregation of chromium, iron, and lead, reaffirming this shared anthropogenic etiology. The third PCA component was characterized by selenium, followed by arsenic and magnesium in the fourth. The resultant PTE contamination underscores a profound ecological and public health risk, impacting both the aquatic ecosystems and the local community within the precincts of the Matjhabeng Local Municipality (MLM) area, with consequential amplification of susceptibilities to deleterious health consequences. Urgent and concerted interventions are imperative to ameliorate the emergent decline in surface-water quality within the MLM locale. The adoption of nature-based remediation paradigms holds promise for efficaciously elevating water quality, ameliorating community health, and underpinning the long-term economic viability of the region.