Lacquerware, as one of the important symbols of the Chinese national culture, has long been a focus of conservation researchers. We took a Southern Song lacquerware fragment, unearthed in Wenzhou, Zhejiang Province, and decorated with carved patterns filled with paints, as the research object, and studied it using digital microscopy, upright fluorescence microscopy, SEM-EDS, micro-Raman spectrometry, FT-IR and Py-GC/MS. This work shows the micro-destructive analysis process of the complex matrix material/composition, structure and lacquering techniques for multilayer lacquerware. We summarize methods to detect commonly used materials in lacquerware. This article provides technological support for the research on lacquerware.