The invention discloses guaiazulene and an extraction process thereof. The extraction process comprises the following steps: distilling and vacuum collecting natural essence and fragrance oil comprising an azulene compound, and obtaining a fraction A; dehydrating the fraction A, decompression distilling, and obtaining a fraction B; dehydrogenating the fraction B, vacuum distilling, and obtaining an azulene-containing mixed solution; adding an acid solution B and organic solvent into the azulene-containing mixed solution, uniformly mixing, standing, layering, uniformly mixing and stirring the acid layer solution, cold water A and petroleum ether, settling, discharging the acid water, filtering the residues, placing the residual solution into a recycling kettle, adding cold water B into therecycling kettle, slowly heating until all petroleum ether is completely distilled, cooling, standing, layering, removing the moisture, and obtaining a guaiazulene crude product; and crystallizing andfiltering the guaiazulene crude product, and obtaining a guaiazulene pure product with the purity being 99 percent or above and the yield of 2.9 to 3.6 percent. The extraction process is safe, and environmentally friendly, and prepared guaiazulene is high in purity and high in yield.