A membrane-aerated biofilm reactor (MABR) combines membrane technology with biofilm processes and has unique advantages in the treatment of organic wastewater and volatile wastewater. The common membranes for MABR systems usually have relatively uneven pore structures and low bubble point pressure, resulting in unsatisfactory O2 utilization and wastewater treatment efficiency. In this work, polydimethylsiloxane (PDMS) and UiO-66 (a Zr-based metal organic framework) were coated on the surface of a commercial polypropylene (PP) hollow fiber membrane to prepare oxygen-rich MABR membranes and modules, which showed an attractive O2 utilization rate and wastewater treatment efficiency. The bubble points of the PDMS and PDMS-UiO-66 membranes were significantly higher than those of the PP membranes, and the PDMS-UiO-66 membranes had better oxygen enrichment capacity and biological affinity. The optimal PDMS-UiO-66 membrane modules had an O2 permeance of 31.65 GPU (1 GPU = 3.35 × 10-10 mol m-2 s-1 Pa-1), with O2/N2 selectivity of 2.21. The membrane hanging effect and processing capacity for domestic sewage were greatly improved. This study may provide insights and guidelines to fabricate porous mixed matrix membranes and modules in the industry for MABR. The developed products are expected to be applied in the actual separation process.