In ancient times, drying oils and other additives were usually added to raw lacquer in the manufacture of lacquerwares for the purpose of improving the performance of lacquer film. In order to determine the types of the raw lacquer and additives, we first used thermally assisted hydrolysis-methylation pyrolysis-gas chromatography/mass spectrometry (THM-Py-GC/MS) to analyze the reference sample, and then applied the verified methods and experimental conditions to the study of ancient lacquerwares.The results show that 3-pentadecylcatechol(C15), 3-pentadecenylcatechol(C15:1), which are characteristic components of raw lacquer tapped from Rhus vernicifera, lacquer trees grown mainly in China and Japan, were found in the ancient samples. The type of raw lacquer was determined accordingly. In addition, some fatty acids such as palmitic acid, stearic acid, heptanoic acid, octanoic acid and azelaic acid were detected in the ancient lacquerwares, which are typical components of drying oil, indicating that drying oil was added to the lacquer films. Moreover, three-dimensional video microscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD) were applied to reveal the lacquer-making techniques of the ancient lacquerwares described here. Ancient lacquerers applied ash, primer and color paint on the lacquer bodies successively. The black pigment is an iron compound, and the lacquer ash is made from lacquer, albite and quartz.