Industrial effluents with high concentrations of toxic heavy metals are of great concern because of their persistence and non-degradability. However, poor operation and maintenance of wastewater treatment infrastructure is a great concern in South Africa. In this study, physico-chemical parameters and heavy metals (HMs) concentration of wastewater from five different industries, Leeuwkuil wastewater treatment plant (WWTP) inflow and effluent, and Vaal River water samples were monitored between January and September 2017, to investigate the correlation between heavy metal pollution and the location of industries and ascertain the effectiveness of the municipal WWTP. Physico-chemical variables such as pH, biological oxygen demand (BOD), dissolved oxygen (DO), chemical oxygen demand (COD), total dissolved solids (TDS) and electrical conductivity (EC) exhibited both temporal and spatial variations with the values significantly higher in the industrial samples. Inductively coupled plasma optical emission spectrometry (ICP-OES) results also showed that aluminium (Al), copper (Cu), lead (Pb) and zinc (Zn) were significantly higher in industrial effluents (p < 0.05), with only Zn and Al exhibiting significant seasonal variability. Statistical correlation analysis revealed a poor correlation between physicochemical parameters and the HMs compositional quality of wastewater. However, toxic HMs (Zn, Cu and Pb) concentrations in treated wastewater from WWTP were above the permissible limits. Although the WWTP was effective in maintaining most of the wastewater parameters within South African Green drop Standards, the higher Cu, Zn, Pb and COD in its final effluent is a concern in terms of Vaal river health and biological diversity. Therefore, we recommend continuous monitoring and maintenance of the WWTPs infrastructure in the study area.