A new and green vortex-assisted supramolecular solvent liquid–liquid microextraction (VA-SMS-LLME) method has been advanced to pre-concentrate and assess mecury in different environmental and biological samples. The proposed approach was dependent on utilisation of quinalizarin as a chelating agent to form mercury-quinalizarin complex at pH 7.0 which extracted into (1-decanol/THF) as supramolecular solvent (SMS). The extracted complex was centrifuged and determined spectrophotometrically at λmax = 570 nm. The final experimental conditions including pH, amount of quinalizarin, type and volume of supramolecular solvent, centrifugation and vortex conditions, sample volume and matrix effects were studied and optimized. The calibration graph was linear within 1.0–100 μg L−1 concentration range. The limit of detection, preconcentration factor and relative standard deviation were 0.30 μg L−1, 100 and 1.80%, respectively. The validation of the developed VA-Ss-LLμE procedure was acheived by the analysis of (NIST-1641d mercury in natural water and NCS ZC81002B human hair) certified reference materials. The proposed approach was applied to the determination of mercury in real water, food and hair samples successfully.