A novel dual-functional catalytic perovskite hollow fiber membrane reactor was fabricated by integrating BaBi0.05Co0.8Nb0.15O3-δ (BBCN) perovskite hollow fiber membrane with Ni-phyllosilicate hollow sphere catalysts for simultaneous NO decomposition and partial oxidation of methane (POM) reaction. With this novel catalytic membrane reactor, NO could be completely converted to N2 at a medium-low temperature (675 °C) owing to instantaneous oxygen removal from the NO decomposition reaction system. Coupled POM reaction on the other side of BBCN hollow fiber membrane not only increased the driving force for oxygen permeation but also produced valuable products (syngas). This novel membrane reactor showed high NO removal capacity at comparatively low temperatures (675-700 °C), which is 100-200 °C lower than those of other membrane reactors reported in literature. In addition, even with the presence of a 2-5% oxygen concentration in NO stream, NO could still be completely decomposed to N2 via this catalytic BBCN membrane reactor. Evidently, the application of this novel catalytic membrane reactor could overcome the inhibition of oxygen present atmosphere for NO decomposition and achieve a remarkably high efficiency for NO removal.