The lacquer scabbard of a bronze sword dating from the Warring States (476–221 BCE) and excavated from a Ba tomb of the Lijiaba site (Chongqing, southwest China) was characterized by a multidisciplinary approach including microscopy, scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDS), Raman spectroscopy and pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS). Pyrolysis-comprehensive two-dimensional gas chromatography/mass spectrometry (Py-GCxGC/MS) has been applied for the first time for the characterization of a valuable archaeological lacquer sample confirming the benefits of this technique for the description of the ingredients used in the formulation of the lacquer coating. Besides, the analytical results also showed that, in accordance with what is suspected from the lacquer technique employed at this period, two lacquer film layers and a bone-derived ground layer were present as confirmed by the characterization of hydroxyapatite particles (Ca5(PO4)3OH) of different sizes. Py-GC/MS analysis allowed identification of the origin of the scabbard lacquer as a Toxicodendron vernicifluum lacquer and detection of potential drying oil markers, while Py-GCxGC/MS analysis revealed the presence of a series of polyaromatic hydrocarbons (PAHs) compounds non-characterizable by 1D GC/MS analysis. This latter observation highlights the use of soot attributed to a plant origin in conjunction with bone for the manufacture and coloring of the lacquers.