The invention discloses a roasting pretreatment process for extracting vanadium pentoxide from a high-carbon scherbinaite-containing coal mine and a vanadium pentoxide extracting method, which comprise the following steps that: the stone coal scherbinaite is used as raw materials, the raw materials are crushed and pressed into blocks and are dried, then, the materials are continuously put into a tunnel kiln capable of regulating the air volume and the pushing speed to be roasted, the temperature is controlled between 400 DEG C and 1000 DEG C in the roasting process, the roasting time lasts 7hto 40h, and the pretreatment process is completed after the roasting. The roasting products are crushed, and then, vanadium pentoxide products are obtained sequentially through leaching, neutralization, oxidization, impurity removal, enrichment, ammonium salt vanadium deposition and calcination. The process has the advantages that the application range is wide, the energy consumption is low, the heat value utilization is sufficient, the equipment investment is low, the environment pollution is little, and the like. The method is suitable for being applied to the vanadium pentoxide extraction from the high-carbon scherbinaite-containing coal mine.