The invention discloses a double-metal co-doped carbon nano-composite material and a preparation method thereof. The composite material is prepared from a carbon substrate and ferrocene-phenylalanine and transition metal except iron, which are co-assembled on the carbon substrate through a non-covalent bond, wherein the ferrocene-phenylalanine, the transition metal except the iron and the carbon substrate commonly form a raspberry-like nanosphere structure. The invention further discloses a double-metal-nitrogen-carbon nano-catalyst obtained by mixing the composite material with dicyanodiamide and carbonizing and further provides application of the double-metal-nitrogen-carbon nano-catalyst to catalytic oxygen reduction reaction. The preparation methods of the composite material and the catalyst have simple steps and low cost and are suitable for large-scale application. The double-metal-nitrogen-carbon nano-catalyst provided by the invention has excellent electrochemical performance and has good methanol toxin resistance and stability, so that the double-metal-nitrogen-carbon nano-catalyst has a good application prospect in the field of the catalytic oxygen reduction reaction.