This work presents a new, fast and simple method for the determination of fullerene C₆₀ aggregates (nC₆₀) in environmental waters by vortex-assisted liquid–liquid microextraction (VALLME) and liquid chromatography-mass spectrometry. Vortex agitation accelerated mass transfer from the aqueous sample into the octanol phase and resulted in a short extraction time. Moreover, lowering the pH of the aqueous sample and adding small amounts of salt destabilized nC₆₀ aggregates and facilitated mass transfer into the octanol phase. Several experimental parameters were controlled and the optimum conditions found were: 50 μL octanol as the extractant phase; 20 mL water sample (pH = 4; 1% w : v NaCl); 5 min vortex mixing at 2650 rpm followed by 2 min centrifugation at 3500 rpm. The linearity of the method was found to be good within the range 0.25–2.50 μg L⁻¹ (coefficient of determination, r², 0.9908) and the limit of detection for a signal-to-noise ratio of 3 was 0.08 μg L⁻¹. The relative standard deviations for aqueous solutions containing 0.50 and 2.00 μg L⁻¹ of nC₆₀ were 7% and 3% respectively. The developed method was also applied to tap and effluent wastewater samples spiked with nC₆₀ and the mean relative recoveries were 90 and 79% respectively. Overall, the proposed method is a low-cost and easy to use procedure that allows rapid low-level environmental determination of aqueous fullerene aggregates whilst using small sample volumes and microvolumes of organic solvent.