A series of MnO2 doped Fe2O3 hollow nanofibers with different Mn/Fe molar ratios were successfully synthesized by the electrospinning method for the low temperature selective catalytic reduction (SCR) of NO with NH3 in the presence of excess O-2. The SEM and TEM images showed obvious hollow tubular structure of electrospun nanofibers. The hollow nanofibers with Mn/Fe molar ratio of 0.15 exhibited the highest catalytic activity, nearly 100% of NO conversion from 150 to 300 degrees C, among the catalysts investigated. The TPR, XPS and in situ FTIR results revealed that Mn4+ was the main active species for SCR reaction, and the addition of Mn species enhanced the surface concentration and acidity of Lewis acid sites.