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Simultaneous measurements of interdiffusion and intrinsic diffusion coefficients in liquid Sn-Pb were performed using the shear cell method and a stable density layering. The binary diffusion couples of Sn-Pb and Sn0.6Pb0.4-Sn0.4Pb0.6 were used in two experiments with the average molar fraction of diffusion couples NSn = 0.5. The concentration dependency of the interdiffusion coefficient was confirmed to exhibit a downward convexity through the comparison of the interdiffusion coefficients. However, the Boltzmann–Matano method reveals a diminished influence. The sample measurements of the intrinsic diffusion coefficients of a diffusion couple of pure metals demonstrate a dependency on concentration. On the other hand, the difference of diffusion coefficients was small in a diffusion couple of alloys. The difference between the values calculated by fitting the error function based on the superposition of fluxes and by the conventional analysis methods was small. We propose that a reasonable intrinsic diffusion coefficient can be calculated using the superposed equation of error function. The theoretical interdiffusion coefficients were calculated by substituting the measured intrinsic diffusion coefficients into the Darken’s equation and comparing the results with the measured values. As a result, the difference between the theoretical and measured interdiffusion coefficients is not very large.