In ancient Goryeo celadon, the effect of the chemical composition and ionic state of Fe on the color was evaluated by Mössbauer spectroscopy and Design of Experiment (DOE) analysis. The ancient celadon pieces excavated from the kiln sites in GangJin and Buan areas were analyzed by Mssbauer spectroscopy, chromaticity, and DOE analysis. The color of celadon was found to be mainly determined by that of glaze since variations of L*, a*, and b* values for the body were much smaller than those for the glaze. As Fe 2+ /Fe3+ in glaze increases, L* value increases, whereas a*/b* value decreases, which is well consistent with the result on the synthetic glaze. As the amount of titanium increases in the glaze, the a* and b* values decrease; on the other hand, the L* value increases, which is well consistent with the result on the synthetic glaze.