A supramolecular solvent (SUPRAS) was prepared from undecanoic acid and tetrabutylammonium hydroxide and used as an extraction solvent. A fast microextraction approach based on air-assisted solidified floating organic drop (AA-SFODME) coupled to a hydride generation atomic absorption spectrometer (HG-AAS) for arsenic and selenium traces determination in water and food samples was developed. The air bubbles enhanced the extraction efficiency by reducing both the time and the required chemical amounts. The 2-((4-iodophenyl) diazenyl)-8-hydroxyquinoline (IPHQ) was used as a chelation reagent. The experimental factors that impact extraction efficiency were improved and optimized. The limits of detection (LODs) for arsenic and selenium were 0.09 and 0.07 µg L−1, respectively. Also, the preconcentration factors (PFs) and enhancement factors (EFs) were found to be 100 and 103 for both arsenic and selenium, respectively. The linearity of both two calibration curves ranged from 0.10 to 700 µg L−1, with linear regression coefficients (R2) of 0.9986 and 0.9978, respectively. Finally, the greenness score was determined using two tools: the analytical greenness calculator (AGREE) and the Blue Applicability Grade Index (BAGI). The high greenness scores from these tools can make this method even more environmentally friendly and practical.