||Membranes with exquisite molecular separation capabilities fabricated in the reliable, inexpensive, and scalable platform have potential to be a strong contender for the currently well-established thermal separation processes. Zeolitic imidazolate frameworks (ZIFs), among various metal-organic frameworks (MOFs), with tunable nanopores, show advantageous molecular sieving characteristics and thermal/chemical stability. Interfacial microfluidic membrane processing (IMMP) technique has opened up a way to scalably fabricate ZIF membranes in polymeric hollow fibers that can be packaged into multifilament modules. Here, we created more robust ZIF membranes using macroporous carbon hollow fiber support via IMMP approach. Carbon-supported ZIF membranes synthesized in more aggressive conditions show excellent resistance toward solvent and mechanical instabilities—properties that are critical to the stable separation of biomass-derived molecules for a prolonged period of time. The molecular separation properties of fabricated ZIF-90 and ZIF-8 hollow fiber membranes for butane isomer separation (n-C4H10/i-C4H10), and dehydration of ethanol and furfural were identified and characterized.