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A shard of Chinese underglaze copper-red porcelain from the Yuan dynasty (AD 1271–1368) made in the Jingdezhen kiln was measured by synchrotron radia-tion-induced X-ray fluorescence mapping and X-ray absorption near-edge spectroscopy to investigate the influence of copper element distribution and speciation on the color of porcelain. In black-colored region, copper accumulates at the interface between the body and glaze layers with metallic copper particles as the main speciation. In contrast, Cu is irregularly distributed in the red-colored region with multi-valence speciation. The differences in Cu distribution and speciation in black- and red-colored regions indicate that they are the main factors influencing the different colors of copper-red underglaze porcelain.