A series of complex oxide Cu1-xKxFe2O4 fibers have been prepared via a sol-gel process related electron-spinning procedure, in which x is among 0, 0.05, 0.1 and 0.2 corresponding to the quantity of Cu2+ partial substitution by K+. The average diameter of the fiber was 500 nm. The catalytic activity of the catalysts in removal of NOx and carbon black from diesel exhaust gases were examined in detail using temperature-programmed reaction technique. The results show that after partial substitution of Cu2+ with K+, the catalytic activities have been improved. Cu0.95K0.05Fe2O4 as an optimal catalyst can significantly decrease the ignition temperature (Tig) of the PM, and has high catalytic activity on the removal of NOx.