The invention relates to a composite polymerization inhibitor for extracting and rectifying conjugated diene with dimethylformamide, and a use method. The composite polymerization inhibitor is characterized in that the inhibitor comprise a component A and a component B, wherein the component A is a mixed solution prepared by dissolving 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen, 2-hydroxyl ethylamine and an adjuvant in toluene; a weight concentration of 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen in the mixed solution is 10-20%; a weight concentration of 2-hydroxyl ethylamine in the mixed solution is 20-40%; a weight concentration of the adjuvant in the mixed solution is 5.0-20%; the adjuvant is alcohol, propyl alcohol, isopropanol, isobutanol, tertiary butanol or phenethyl alcohol; and the component B is a sodium nitrite aqueous solution with a weight concentration of 10-30%. The components of the polymerization inhibitor have synergistic effects, the polymerization inhibitor has a good polymerization inhibition effect, is not deposited in a tower, is convenient and accurate to use, is not crystallized and is freeze-resistant in a low temperature environment, and the consumption of a solvent is low.