Protoporcelain is a kind of multi-epoch and multi-culture-area ceramic hangover with iterative appearance, and it is the important interim of the development from pottery to porcelain. Therefore, its origin, development and prevalence problems, which relate directly to China development mode and Shang Zhou culture visage, are the important discussion of archaeology, ceramic technic history and chemistry history, and have important learning value. XRF and XRD technique were used to determine several shreds excavated from Yingguo graveyard site in Henan province. The result shows that some samples have abnormity phosphor, hinting that some plant or wood ash was ever used as raw material. From the rate of Ca/Al and P/Al and comparative analysis, we discovered that proto-porcelain of Yingguo site has different chemical character compared to south production.