In this work, in situ polymerization of modified sol-gel silica in a polyether sulfone matrix is presented to control the interfacial defects in organic-inorganic composite membranes. Polyether sulfone polymer and modified silica are used as organic and inorganic components of mixed matrix membranes (MMM). The membranes were prepared with different loadings (2, 4, 6, and 8 wt.) of modified and unmodified silica. The synthesized membranes were characterized using Field emission electron scanning microscopy, energy dispersive X-ray, Fourier transform infrared spectroscopy, thermogravimetric analyzer, and differential scanning calorimetry. The performance of the membranes was evaluated using a permeation cell set up at a relatively higher-pressure range (5�30 bar). The membranes appear to display ideal morphology with uniform distribution of particles, defect-free structure, and absence of interfacial defects such as voids and particle accumulations. Additionally, the CO2/CH4 selectivity of the membrane increased with the increase in the modified silica content. Further comparison of the performance indicates that PES/modified silica MMMs show a promising feature of commercially attractive membranes. Therefore, tailoring the interfacial morphology of the membrane results in enhanced properties and improved CO2 separation performance. © 2022 by the authors.