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The microstructural changes occurring during drawing and ageing in pearlitic steel wires have been studied using the thermoelectric power (TEP) measurements combined with atom probe tomography (APT) and differential scanning calorimetry (DSC). APT analysis confirmed that cementite dissolution occurs during the cold-drawing process. The high sensitivity of TEP to solute atoms allowed two ageing mechanisms to be identified, both related to a redistribution of carbon atoms. The complementary use of tensile tests and DSC confirmed these results.