Facilitated extraction membrane processes present a promising technology to replace conventional methods of producing and purifying glycerol. They offer green, ecofriendly, and sustainable platforms with economic benefits. Therefore, in this article, we are interested in improvements to current glycerol purification techniques, in particular, the development of a more efficient, cost-effective, and sustainable glycerol purification process. The current work presents studies relating to the use of three polymer inclusion membranes (PIMs) constituted by poly(vinyl alcohol) (PVA) as a polymer support and the extractive agents resorcinarene C-undecylcalix (4) (Res), dibenzo-18-crown-6 (Crw), and β-cyclodextrin (β-CD). The developed membranes are adapted to facilitate the extraction of glycerol using a separation technique based on the principle of membrane oriented membrane processes. Kinetic and thermodynamic models based on the interaction between the glycerol substrate and the extractive agent immobilized in the membrane phase were adopted for the determination of macroscopic, microscopic, and activation parameters. The computational approach based on the threedimensional representation of the molecules allowed us to elucidate the mechanism with probable interactions the movement nature of glycerol molecules and to explain the experimental values. All results showed that the Res extractive agent is more efficient than its agent counterparts Crw and β-CD, with apparent diffusion coefficient values (10 5 D*) of 18.03, 2.99, and 1.65 cm 2 •s −1 respectively at 308 K. The membranes adopted and tested for the extraction oriented processes of the glycerol compound from an algae extract show a high performance for the PVA/β-CD membrane with a purity of 98.4%, whereas for glycerol extracted through the PVA/Crw and PVA/Res membranes these purities are 85.2% and 78.8%, respectively. The results described for the quantification of oriented processes relating to the facilitated extraction of the glycerol compound are unpublished in the literature and present original studies necessary to develop and optimize a clean and sustainable technique for obtaining pure glycerol.