Plastic fragments of size range 1µ - 5000µ categorised as microplastics (MPs) are becoming ubiquitous in almost every environmental compartment. Hence, the potential threats of these microplastics to aquatic organisms, birds, mammals, and even human beings via mistaken ingestion or food webs is becoming an issue of concern. Besides their adverse effects on the freshwater aquatic organism by ingestion, microplastics are adsorbent vectors for water pollutants due to their diverse functional properties. However, this vector effect in natural environmental waters with various water quality criteria remains unclear. Therefore, to understand this issue, especially in freshwater ecosystems, it is vital to investigate the adsorption of contaminants of emerging concern on the microplastics and their concentration. Focusing mainly on lower-order rivers, which are critical pathways for transporting plastic fragments to ocean waters. Effective and reliable extraction methods are required to assess the sorption process of contaminants from microplastics. In this study, we investigated the adsorption of three pharmaceuticals (Sulfamethoxazole, ciprofloxacin, 17β- estradiol) to polyethene Terephthalate (PET) MPs in Bloukrans River waters using high-resolution liquid chromatography–mass spectrometry LC-MS/MS equipped with a triple quadrupole (QqQ) analyser. The results showed that MPs could enrich pharmaceuticals from the surrounding waters. All three drugs occurred at quantifiable concentrations, with the highest reported concentration of Sulfamethoxazole (353.1±395.18ng/l), ciprofloxacin (10984.27±12172.69ng/l), 17β-estradiol (44.105±14.80ng/l) on the retrieved MPs particles. The concentration of the three MPs chemicals was significantly associated with seven or more of the ten water quality criteria. The highest concentration of the pharmaceuticals was found in waters from domestic waste refuse sites, the primary recipient of sewage effluents from Makhanda municipality. These findings are essential to understanding MPs' effects, especially the increased combined toxic effects on aquatic life and associated ecological risks.