Crosslinked polymer gels are gaining technological and industrial attention due to their sophisticated application features. Herein, a highly effective amphiphilic polymeric network capable of absorbing polar and nonpolar solvents was produced using hydrophilic glycerol ethoxylate, a member of star type polyethylene glycol (s-PEG), and different hydrophobic organosilane monomers by bulk polymerization as utilized under an inert atmosphere. In this context, the preparation of amphiphilic polymeric networks was achieved by the reaction between hydroxyl terminated s-PEG and ethoxysilane terminated organosilane without using any initiator, activator or a catalyst. SEM, FTIR, 13C and 29Si CPMAS NMR and TGA are used for morphological, structural and thermal characterization of the prepared materials. Likewise, the absorption behavior of amphiphilic polymeric networks was determined by measuring their swelling ratios in polar and nonpolar solvents. Because of having a hydrophobic and hydrophilic structure in their 3D polymeric structure, the obtained polymeric networks behave as an organogel in oil medium, while they can prepared as a hydrogel in aqueous medium. The effect of crosslinker’s difference on the swelling capacity of sorbent were researched by comparing different molecular weight of monomers, and it was found that the molecular structure of organosilane monomers had significant influence on the swelling ability of obtained amphiphilic sorbents. By the use of easy preparations, not needing extra agents for the synthesis, having high and quick absorption abilities in organic solvents showed that the resulting amphiphilic sorbent have potential as absorbents for different organic solvents. Also, the degradable features of amphiphilic polymer networks in water open up optimum application opportunities for additional uses, such as with drug delivery agents.