In this paper, the interdiffusivities in fcc Co-Ni alloys at 1373 K due to different types of diffusion couple experiments were firstly re-calculated via the unified Wagner method based on the measured composition profiles. Their maximum difference due to different approaches for diffusion couple preparation was found to be larger than one order of magnitude. Then, a comprehensive analysis on the effect of different preparation methods was performed. After that, a two-step diffusion couple technique in combination with the pragmatic numerical inverse method was proposed to determine the accurate interdiffusivities by eliminating the effect of external stress. Such a novel approach was successfully applied in the binary fcc Co-Ni alloys for demonstration purposes. Moreover, it is anticipated that such novel approach can be utilized as the standard method for accurate interdiffusivity measurement, and the resultant accurate interdiffusivities in different alloys may serve as a benchmark for the later experimental and theoretical studies.