The invention discloses a preparation method of a nitrogen-doped graphene/copper sulfide/hollow sulfur composite material. The preparation method comprises the following steps: step (1), adding powdered sulfur into carbon dioxide, stirring and dissolving to form a uniform solution; step (2), ball-milling high-purity nickel powder through a high-energy ball grinding mill, adding the high-purity nickel powder after ball-milling into the solution, stirring to form uniform suspension liquid, mechanically stirring, and carrying out spray drying to form sulfur clad spherical particles; step (3), adding the spherical particles into a ferric chloride solution, stirring for reaction, washing and filtering; and step (4), adding a filtered precipitate into a solution containing copper chloride, thioacetamide and a surface active agent, stirring to form uniform suspension liquid, heating and stirring for reaction, centrifuging and washing to obtain copper sulfide clad sulfur particles. In the composite material, a space is reserved for the volume expansion, in the charging and discharging process, of sulfur material through the design of a hollow structure, so that the electrochemical performance can be effectively improved.