Mixed matrix membranes (MMMs) were fabricated by the hydrothermal synthesis of ordered mesoporous KIT-6 type silica and incorporating in polyimide (P84). KIT-6 and MMMs were characterized to evaluate morphology, thermal stability, surface area, pore volume, and other characteristics. SEM images of synthesized MMMs and permeation data of CO2 suggested homogenous dispersion of mesoporous fillers and their adherence to the polymer matrix. The addition of KIT-6 to polymer matrix improved the permeability of CO2 due to the increase in diffusivity through porous particles. The permeability was 3.2 times higher at 30 loading of filler. However, selectivity showed a slight decrease with the increase in filler loadings. The comparison of gas permeation results of KIT-6 with the well-known MCM-41 revealed that KIT-6 based MMMs showed 14 higher permeability than that of MMMs composed of mesoporous MCM-41. The practical commercial viability of synthesized membranes was examined under different operating temperatures and mixed gas feeds. Mesoporous KIT-6 silica is an attractive additive for gas permeability enhancement without compromising the selectivity of MMMs. Figure not available: see fulltext. © 2020, Springer-Verlag GmbH Germany, part of Springer Nature.