Oxygen enriched air is of particular interest for controlling and optimizing the combustion characteristics. The present work aims to prepare industrial spiral wound membrane modules (Ф×L=4 inch ×1m) for oxygen enriched combustion. Polydimethylsiloxane (PDMS) has received considerable attention as a potential membrane material for gas separation due to high intrinsic permeability to gases for many years. In this work, SiO2 nanoparticles were blended with PDMS casting solution to form a hybrid organic and inorganic membrane material. Subsequently, the hybrid casting solution was then coated on polysulfone (PSf) ultrafiltration support membrane to prepare hybrid organic/inorganic gas separation membrane. This would potentially improve the mechanical strength and gas permeability. The average membrane flux and separation factor (O2/N2)could reach1.15 m3/(m2•atm•h) and more than 2.0. Five membrane modules were thereafter equipped for the oxygen enriched combustion in a 4 tons oil-fired boiler. The effect of the oxygen enrichment by the membrane system was on-site assessed. It was noted that 5.7% energy could be saved after using the oxygen enriched membrane system.