The diffusion coefficient (D) and surface transfer coefficient (β) of carbon are important parameters governing the kinetics of carburization, and some other heat treatment processes accompanied by redistribution of carbon in steel. Here, we propose to use an electrical conductivity relaxation (ECR) method for the in situ measurement of D and β of carbon. The feasibility of the method is discussed by the theoretical modeling of carburization for an infinitely long rectangular sample. The synthetic ECR data for the carburization is simulated by tracking the relaxation of electrical conductivity upon a sharp or a gradual change of carbon potential. Then, by Fourier transform, the synthetic ECR data is transformed to an impedance spectroscopy, which is used for estimation of D and β by fitting with a one-dimensional equivalent circuit model. The effects of the width-to-thickness ratio of the sample and the duration of carbon potential buildup on the accuracy of the estimated D and β are studied. The feasibility of the ECR method is verified, and rational guidance for experimental design is proposed.