We developed a facile methodology for fabricating a free-standing mixed-matrix membrane (MMM) containing covalently incorporated vinyl-functionalized UiO-66-CH=CH2 particles up to 60 wt% by utilizing thiol-ene photopolymerization. FTIR, TGA, SEM, EDX, and XRD strongly supported the fact that the desired MMM containing well-dispersed UiO-66-CH=CH2 particles was successfully produced by C–S bond formation. The MMM was highly flexible and showed improved mechanical properties compared to the pristine polymeric membrane, indicating that the covalently immobilized UiO-66-CH=CH2 particles were homogeneously distributed in the polymer matrix. Gas permeability across the MMM was significantly enhanced compared with the pristine polymeric membrane as diffusion of the gas molecules was facilitated in the porous space of the MOF.