The thermal electromotive force (TEMF) and the thermal electromotive force coefficient (TEMFC) of the thermocouple consisting of a copper wire and an (X5CrNi1810) steel wire plastically deformed under tension or bending conditions were found to increase with increasing degree of plastic deformation. The increase in the degree of deformation disturbs the microstructure of steel due to increases in the density of chaotically distributed dislocations and internal microstress, resulting in a decrease in the electron density of states near the Fermi level. Through the effect of thermal energy, annealing at elevated temperatures up to 300 o C leads to microstructural ordering along with simultaneous increases in the free electron density of states, TEMF and TEMFC. Based on the temporal change of the TEMF, the kinetics of microstructural ordering was determined. During the initial time interval, the process is a kinetically controlled first-order reaction. In the second time interval, the process is controlled by the diffusion of reactant species.