State-of-the-art gas separation membrane technologies combine the properties of polymers and other materials, such as metal–organic frameworks to yield mixed matrix membranes (MMM). Although, these membranes display an enhanced gas separation performance, when compared to pure polymer membranes; major challenges remain in their structure including, surface defects, uneven filler dispersion and incompatibility of constituting materials. Therefore, to avoid these structural issues posed by today's membrane manufacturing methodologies, we employed electrohydrodynamic emission and solution casting as a hybrid membrane manufacturing method, to produce ZIF-67/cellulose acetate asymmetric membranes with improved gas permeability and selectivity for CO2/N2, CO2/CH4, and O2/N2. Rigorous molecular simulations were used to reveal the key ZIF-67/cellulose acetate interfacial phenomena (e.g., higher density, chain rigidity,etc.) that must be considered when engineering optimum composite membranes. In particular, we demonstrated that the asymmetric configuration effectively leverages these interfacial features to generate membranes superior to MMM. These insights coupled with the proposed manufacturing technique can accelerate the deployment of membranes in sustainable processes such as carbon capture, hydrogen production, and natural gas upgrading.