Fullerenes engineered nanomaterials are regarded as emerging environmental contaminants. This is as their widespread application in many consumer products, as well as natural release, increases their environmental concentration. In this work, an ultrasonic-assisted pressurized liquid extraction (UAPLE) method followed by high performance liquid chromatography with ultraviolet-visible detector (HPLC-UV-vis) was developed for extraction and determination of fullerene in sediments. The method was validated and found to be suitable for environmental risk assessment. Thereafter, the method was used for the determination of fullerene (C61-PCBM) in sediment samples collected from Umgeni River, South Africa. The current method allows for adequate sensitivity within the linear range of 0.01–4 µg g−1, method limit detection of 0.0094 µg g−1 and recoveries ranged between 67–84%. All the parameters were determined from fortified sediments samples. The measured environmental concentration (MEC) of fullerene in the sediment samples ranged from not detected to 30.55 µg g−1. To the best of our knowledge, this is the first report on the occurrence and ecological risk assessment of carbonaceous fullerene nanoparticles in African sediments and biosolids.