The invention discloses a composite cathode of a microbial fuel cell and a preparation method thereof. The composite cathode in turn comprises a catalytic layer, a carbon cloth layer, a carbon base layer and a diffusion layer from one side to the other side; and the material of the catalytic layer is a mixture of a graphene oxide / magnesium oxide composite material, activated carbon and perfluorinated sulfonic acid. The composite cathode of the microbial fuel cell is prepared from the magnesium oxide / graphene oxide composite material. Compared with noble metal platinum and alloy materials thereof, the raw materials of the composite cathode of the microbial fuel cell are wide in source and low in price, and the prepared composite cathode has a large surface area, excellent conductivity and stable electronic migration, can be used in microbial fuel cells, has low cost, stable operation and high output power, and can be widely used in the microbial fuel cells, lithium batteries or super capacitors.