The invention discloses hollow microspheres with multilayer nickelous sulfide shells, a preparation method and application thereof. The preparation method comprises the following steps: growing a nickel precursor on the carbon sphere surfaces by low-temperature solution precipitation, calcining in air to obtain the hollow microspheres with multilayer nickel oxide shells, and vulcanizing the nickel oxide microspheres in a pipe furnace to obtain the complete hollow microspheres with multilayer nickelous sulfide shells. The unique multilayer-shell hollow structure is beneficial to effective infiltration of the electrolyte, and the electrolyte can sufficiently contact the active substances, thereby enhancing the electrochemical properties of the material. The supercapacitor electrode material prepared from the multilayer-shell hollow nickelous sulfide microspheres has the advantages of favorable electrochemical properties, simple technique and mild conditions.