The present study investigates the potential of novel mixed matrix membranes
that are formed from the biopolymer carboxymethyl cellulose (CMC) and the metal–organic framework ZIF-8 to improve the pervaporation dehydration of isopropanol. The effect of ZIF-8 content variation and porous substrate selection (comprising cellulose acetate (CA) and polyacrylonitrile) on dense and supported membrane properties is systematically investigated using multiple analytical techniques. It is found that ZIF-8 incorporation alters the membrane structure (confirmed by FTIR and NMR), increases surface roughness (observed via SEM and AFM), enhances swelling degree (obtained by swelling measurements), improves surface hydrophobicity (determined by contact angle analysis), and elevates thermal stability (verified by TGA). Quantum chemical calculations are used to validate the interactions between the polymer matrix, modifier, and feed components. The transport properties of developed membranes are evaluated through the dehydration of isopropanol via pervaporation. The cross-linked supported CMC membrane with 10 wt% ZIF-8 prepared on the CA substrate has the optimal performance: permeation flux of 0.136–1.968 kg/(m2h) and >92 wt% water in the permeate via the dehydration of isopropanol (water content 12–100 wt%) at 22 ◦C.