Ionic liquid (IL) mediated gels commonly known as ion gels or ionic gels have received remarkable attention for their advanced application in electrochemical and electromechanical devices, such as actuators, lithium batteries, electric double-layer capacitors, dye-sensitized solar cells and fuel cells. In this work we focused to determine structural properties of thiol-ene crosslinked gels both in organic solvent dimethyl sulfoxide (DMSO) and IL, 1-butyl-3-methylimidazolium bis(fluorosulfonyl)imide (BMIm FSI) combining multifunctional thiol end-crosslinkers and diacrylate monomer via thiol-ene click reaction. We investigated their mechanical properties and internal structure by estimating mesh chain densities calculated from Young’s modulus compression test and nondestructive scattering method of determining mesh size by scanning microscopic light scattering (SMILS) techniques respectively. The mesh densities of the gels were found to be highly dependent on the functionality of the thiol compound both in IL and conventional solvent, DMSO. Finally, we compared the mesh chain densities determined by the two methods and discussed the assumptions to understand the internal structure of these gels.