In order to study the property and performance of LED as RGB primary color light sources on color mixture in visual psychophysical experiments, and to find out the difference between LED light source and traditional light source, a visual color matching experiment system based on LED light sources as RGB primary colors has been built. By simulating traditional experiment of metameric color matching in CIE 1931 RGB color system, it can be used for visual color matching experiments to obtain a set of the spectral tristimulus values which we often call color-matching functions (CMFs). This system consists of three parts: a monochromatic light part using blazed grating, a light mixing part where the summation of 3 LED illuminations are to be visually matched with a monochromatic illumination, and a visual observation part. The three narrow band LEDs used have dominant wavelengths of 640 nm (red), 522 nm (green) and 458 nm (blue) respectively and their intensities can be controlled independently. After the calibration of wavelength and luminance of LED sources with a spectrophotometer, a series of visual color matching experiments have been carried out by 5 observers. The results are compared with those from CIE 1931 RGB color system, and have been used to compute an average locus for the spectral colors in the color triangle, with white at the center. It has been shown that the use of LED is feasible and has the advantages of easy control, good stability and low cost.