AbstractRecycling water from flue gas of coal‐fired power plants is of great significance to save energy and water resources and reduce environmental pollution. In the present work, two potential polymers (polyether block amide 2533(PEBAX 2533) and sulfonated poly(ether ether ketone) (SPEEK)) were investigated and showed high water vapor permeability and selectivity, respectively. Combined with the advantages of the two materials, a novel PEBAX 2533/SPEEK composite membrane with an ultra‐thin SPEEK selection layer on the outer surface of the high permeable PEBAX 2533 layer was prepared by dip coating. The composite membranes were assembled into a membrane capsule module and tested directly in artificial and real flue gas. The condensed water vapor fluxes were 1006.9 g/m2.h in artificial flue gas and 600–900 g/m2.h on average in real flue gas during a period of 30 days, exhibiting good water vapor permeability and durability in real flue gas.