To reveal comprehensive information and explore scientific methods for classification and provenance recognition of ancient Chinese blue and white porcelains, X-ray fluorescence (XRF) spectroscopy combined with optical coherence tomography (OCT) is used to study the glaze cross-section structure of blue and white porcelains excavated from the Nan′ao No. 1 shipwreck in the Ming dynasty of China. The characteristics of glaze cross-section structures and chemical compositions of glaze, body and cobalt pigment are obtained. The experimental results show that the blue and white porcelain samples originated from Jingdezhen and Zhangzhou are different in terms of glaze cross-section structure and chemical composition of glaze, body and cobalt pigment. According to the obvious difference of white glaze cross-section structures and chemical compositions of body and blue pigment, the blue and white porcelain samples originated from Zhangzhou can be divided into two types made by different kilns. In addition, the blue decorative pattern of blue and white porcelain samples originated from Jingdezhen is studied by three-dimensional scanning function of OCT, which indicates that the combination of OCT and XRF is validated as an effective method to study the classification, provenance and access to comprehensive information of ancient Chinese blue and white porcelains.