The invention relates to a preparation method and application of a carbon nanofiber, tin disulfide, tin dioxide and sulfur composite material with a heterojunction structure, and belongs to the technical field of an energy material. The method comprises the following steps: 1, dissolving tin tetrachloride, thioacetamide and carbon nanofiber into polypropyl alcohol and performing hydrothermal reaction to obtain a carbon nanofiber, tin disulfide and tin dioxide composite material with the heterojunction structure; 2, dipping the composite material obtained in the step 1 into a sulfur solution, taking out after 5 minutes, vacuum-drying and calcining at high temperature to obtain the carbon nanofiber, tin disulfide, tin dioxide and sulfur composite material with the heterojunction structure. The preparation method and the application of the carbon nanofiber, tin disulfide, tin dioxide and sulfur composite material with the heterojunction structure have the following advantages: the composite material has special interface effect, can effectively increase electrode surface electron and ion transmission speed and is favorable for realize efficient utilization of the sulfur and obtainingthe cyclic stable lithium sulfur battery. The composite material can be prepared by directly utilizing a one-step hydrothermal method, the preparation method is simple and practical, and the components are controllable.