CO2 capture via an oxy-fuel route through the U-shaped (Pr0.9La0.1)(2)(Ni0.74Cu0.21Ga0.05)O4+ (PLNCG) hollow fiber membrane with 100% CH4 conversion and 100% CO2 selectivity for 450 h has been explored for the first time. X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy characterizations of the spent hollow fiber membrane have also been investigated. All these results indicate that PLNCG hollow fiber membrane shows excellent reaction performance and good stability under oxy-fuel reaction conditions, which will be a potential rounte for reducing CO2 emissions worldwide. (c) 2013 American Institute of Chemical Engineers AIChE J, 59: 3856-3862, 2013