This paper proposes a colorimetric characterization method using the color correlation between the colorants in a hi-fi printer. While several colorant combinations can be used to match a certain color stimulus in a hi-fi printing system with more than 3 colorants, conventional colorimetric characterization methods only use 3 or 4 colorants to render a color, thereby limiting the color representation. As a result, the gamut is limited as they give up the other combinations of colorants. Therefore, this paper proposes a method of colorimetric characterization that uses combinations of all the colorants. As such, certain colorant combinations are selected based on considering the correlation factor between the colorant amount distributions. The correlation factor also affects the interpolation error, as the colorants are not independent of each other. Consequently, the total gamut is increased in low lightness regions, and the colors are represented more accurately.