In order to explore nondestructive methods to analyze colored Chinese porcelains, we used spectroscopy and optical methods to reveal the macroscopic and microscopic characteristics of two kinds of famous colored porcelains, namely, Doucai (clashing color porcelain) and famille-rose porcelain. We also discuss the technology used to make them. We carried out comprehensive analyses on four Doucai shards from Jingdezhen, Jiangxi Province, and two shard samples with famille-rose decoration from Xinjiang County, Shanxi province, using individual point sampling and comparative study. With the aid of multi-spectral imaging, stereomicroscopy, optical coherence tomography (OCT), X-ray fluorescence spectrometry (XRF) and laser Raman spectrometry, we found that the two kinds of porcelains obviously differ in the chemical compositions of their over-glaze decorations and ceramic glazes. The over-glaze decorations of the Doucai contain a high content of lead, whereas those of the famille-rose porcelains contain arsenic besides lead. For the Doucai, the deep red, green and blue over-glaze decorations were colored respectively with hematite, copper iron and cobalt. For the famille-rose porcelains, the red over-glaze decorations were colored with hematite and the deep red one with cinnabar. Multi-spectral imaging technology was applied to identify and analyze some hidden image information about the over-glaze decoration, and OCT was used to visually observe the cross-section structure of the over-glaze decorations. This study provides a scientific basis for the identification of the porcelain-making technologies of the early porcelains with over-glaze decorations, and also provides a useful methodological reference for the future scientific research. Therefore, the scientific analyses of these two kinds of distinctive porcelains are of great significance in understanding the development of ancient ceramic technologies of China.