The invention discloses a polypyrrole-coated hollow porous cobalt manganate-loaded sulfur composite material, a preparation method thereof, a positive electrode of a lithium-sulfur battery and a lithium-sulfur battery. According to the polypyrrole-coated hollow porous cobalt manganate-loaded sulfur composite material, the preparation method thereof, the positive electrode of a lithium-sulfur battery and the lithium-sulfur battery, ZIF-67 and potassium permanganate are dispersed in an aqueous solution; by means of a hydrothermal reaction, obtained cobalt manganate powder has a dodecahedral hollow structure; a cobalt manganate/sulfur composite material is prepared through a sulfur fumigation method; the outer surface of the composite material is coated with a polypyrrole conductive layer, sothat the cycling stability and rate capability of the lithium-sulfur battery are improved; the hollow structure can accommodate more adsorbed sulfur, so that a sulfur loading quantity can be improved; the cobalt manganate has active sites for strongly adsorbing polysulfide, so that the shuttle effect of the polysulfide between a positive electrode and a negative electrode can be effectively relieved; the outer-layer conductive polymer can enhance the conductivity of the composite material, so that the conductivity of the positive electrode of the lithium-sulfur battery is improved, the shuttle effect of the polysulfide between the positive electrode and the negative electrode is relieved, and the cycling stability and rate capability of the lithium-sulfur battery are enhanced.