This research article proposes a simple, quick, green and cheap approach for the determination of total selenium in food samples using alcohol-DES based vortex-assisted homogenous liquid-liquid microextraction (alcohol-DES-VAHLLME) combination with hydride generation atomic absorption spectrometry (HG AAS). Analyte, complexing agent and working pH were Se(IV), Sudan-II and pH 4.0, respectively. In order to analyze the nature of the chemical interaction between Se(IV) ion and Sudan-II ligand, experimental results were supported with computational chemistry tools calculating quantum chemical descriptors like frontier orbital energies, hardness, softness, electronegativity, electrophilicity, nucleophilicity, transferred electron from the ligand to ion, electron donating power, electron accepting power, complexation energy, molecule-ion interaction energy. In addition, the alcohol-DES-VAHLLME method was earned a good detection limit of 3.5 ng L-1 and a wide calibration curve in the concentration range of 12-300 ng L-1 (r: 0.9981). The validity of the method was evaluated by analyzing the two standard reference material (SRMs). The recoveries and relative standard deviations for 25 and 100 ng L-1 of Se(IV) (N:5) were in the range of 1.2-2.5% and 92.1-103.7% respectively, which proved acceptable. The analytical results showed that the proposed method had important features such as cheapness, green, quick extraction and reuse, which made it attractive for the determination and efficient extraction of total selenium in the food samples.