The invention provides a method for preparing 5-methylthienyl-2-thiol from levulinic acid, relating to thiophene compounds. The method comprises the following steps: adding levulinic acid into a solvent, and adding a Lawesson reagent to react; washing the product with an alkali, neutralizing 4-methoxyphenylphosphonic acid to obtain a salt, and transferring the salt into a water phase, wherein the target product 5-methylthienyl-2-thiol is retained in an organic phase and separated from the 4-methoxyphenylphosphonic acid; and carrying out reduced pressure distillation on the organic phase to obtain the 5-methylthienyl-2-thiol. The raw material reacts with the Lawesson reagent, and the 5-methylthienyl-2-thiol can be prepared by a cascade thionation-cyclization-isomerization process in one reaction procedure, so the steps are simple. The sodium carbonate or sodium bicarbonate solution is used for washing, so that the Lawesson reagent residue 4-methoxyphenylphosphonic acid can be effectively removed on the premise of not influencing the target product 5-methylthienyl-2-thiol. The obtained product has abundant reaction sites, such as aromatic thiophene rings, mercapto groups and the like, and has high plasticity.