Zeolitic imidazolate framework (ZIF‐8, Zn(2‐meIm)2) and composites based on ZIF‐8 and alumina nanofibers (NafenTM), i.e. ZIF‐8/Nafen, were demonstrated to be efficient heterogeneous catalysts for the reaction of methanol with propylene oxide to produce propylene glycol methyl ether (PGME), which is a member of the family of glycol ether solvents used for a wide variety of consumer products and industrial applications. Both the reaction rate and the selectivity toward PGME were found to decrease with increasing crystal size of the ZIF‐8 material, which was related to the change in the number of basic sites and their accessibility. The investigation of ZIF‐8/Nafen composites revealed the dependence of their catalytic performance on the amount of the ZIF‐8 component. In particular, the activity was affected by the crystal size of the ZIF‐8 material and the nature of acid‐base sites in its framework.