The provenance study of ancient ceramics, as an important part in archaeological field, is the researching focus for researchers in scientific and technological archaeology. At present, the provenance study of ancient ceramics mainly depends on chemical analysis technologies while non-destructive physical structural analysis of ceramic glaze is relatively lacking. Therefore, it is difficult to have a comprehensive understanding of ancient ceramics. Optical coherence tomography (OCT) is an emerging non-destructive imaging technology with a high sensitivity. In this paper, the OCT combined with X-ray fluorescence spectroscopy (XRF) is employed firstly to analyze celadon wares of Jingdezhen and Longquan found in Nanhai No.1 shipwreck which is dated to early Southern Song dynasty non-destructively. First, the glaze cross-section structures and decoration characteristics of the celadon wares of the two kilns, Jingdezhen and Longquan,are studied by OCT.The type,thickness of glaze, the glaze inclusions including bubbles, crystals, residual grains, and the cracks on the glaze surface are analyzed based on the OCT images obtained. The characteristics of glaze cross-section structures for the celadon wares of two kilns are compared, and the decoration technologies of the celadon wares are also determined. Next, the chemical compositions of glaze and body of the celadon wares of the two kilns,Jingdezhen and Longquan, are obtained by XRF and compared. Then, the relationship between the differences of glaze cross-section structures and chemical compositions of glaze are discussed. The results show that the celadon wares from Jingdezhen and Longquan are different in glaze cross-section structures, and are the chemical compositions of the glaze and body. Meanwhile the differences of glaze chemical composition are relevant to the differences of glaze cross-section structures. This paper shows that the combination of OCT and XRF is validate as an effective method to identify the porcelains from different kilns.