The invention discloses a compound oxygen reduction electro-catalyst of carbon nano materials modified by macrocyclic compound containing nitrogen and a preparation method thereof, wherein the catalyst is prepared by mixing the macrocyclic compound containing nitrogen and the carbon nano materials completely, and has excellent catalytic activity and stability in cyclic voltammetry. The peak potential of the catalyzing oxygen reduction reaction can reach -0.1V (vs. Ag / Agcl); the peak current density of the oxygen reduction can reach 3.4mA.cm<-2>; the catalyst has stable catalytic activity which is basically not attenuated after 10000 times of cyclic voltammetry; the current generated in the catalyzing oxygen reduction reaction is not affected by the additional organic micromolecules (such as glucose, methanol and formaldehyde) and carbon monoxide. The electro-catalyst has simple preparation process, low cost, and good catalytic activity, selectivity, mithridatism and stability, can be applied to biomembrane electrode reactors, biosensors, fuel cells and other fileds.