Displays with different primary sets were found to introduce perceived color mismatch between stimuli that are computationally metameric and to affect the variations of the perceived color difference of metameric stimuli among observers (i.e., observer metamerism). In this study, computational analyses and psychophysical experiments were carried out to investigate the possibilities of increasing the color gamut area of a commercially available liquid crystal display (LCD) system using 16 three-primary sets, so that the perceived color difference of the white point between the system and the reference display and observer metamerism can be minimized. It was found the primary set with the peak wavelengths of 450, 525, and 665 nm was able to increase the sRGB color gamut by 72.1% in the CIE 1931 chromaticity diagram, which was found to have a strong correlation to the color volume of wide color gamut displays, while introducing the minimal color mismatch to the white point of the reference display and observer metamerism. The small white point color mismatch could be due to the similar wavelengths of the blue and green primaries in comparison to the reference display. In addition, the experiment results suggested that the CIE 2006 2° Color Matching Functions (CMFs) had better performance in characterizing the color match of the white point than the CIE 1931 2°, 1964 10°, and 2006 10° CMFs, which could be due to the fact that the stimulus used in the experiment only had a field of view (FOV) around 3.8°.