The Prince Kung's Palace Museum is the largest and most well-preserved Qing dynasty princely residence, with its mansion area having been used successively as the residence of “GuLun-HeXiao” Princess (Heshens residence), Prince Qings Mansion, and Prince Kungs Mansion. Baoguang Hall served as the private reception hall for Prince Kung during his time. According to archival records, most of the existing polychrome paintings in Baoguang Hall date back to the mid-Qing period. Previous research on the polychrome paintings of the Prince Kungs Palace Museum has primarily focused on their form and aesthetic style, with little scientific analysis conducted on their production techniques and materials. This study utilizes a suite of analytical techniques, including depth-of-field microscopy, polarized light microscopy, laser Raman spectroscopy, and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, to analyze and identify the pigments used in the polychrome paintings from Baoguang Hall. The results showed that the cyan pigments of the color painting of the Baoguang Hall were azurite ［2CuCO3·Cu(OH)2］, indigo (C16H10N2O2), Prussian blue (Fe4［Fe(CN)6］3), lazurite (Na8Al6Si6O24Sn), artificial ultramarine (Na8Al6Si6O24Sn) and Smalt (CoO·nSiO2). The green pigments were copper chloride hydroxide ［CuCl2·3Cu(OH)2］. The red pigments were vermilion (HgS), red lead (Pb3O4), and iron red (Fe2O3). The yellow pigments were orpiment (As2S3). The white pigments were chalk (CaCO3), kaolin ［Al2Si2O5(OH)4］ and lead white［2PbCO3·Pb(OH)2］. The black pigments were carbon (C). Additionally, the study found a prevalent use of multi-layered polychrome paintings and mixed pigments. The pigments application dates are mostly concentrated in the mid-Qing period, indicating that most of the extant polychrome paintings are likely remnants from this era, consistent with the documented period of their creation. This study represents the first scientific analysis of the production techniques and materials of the polychrome paintings in the Prince Kungs Palace Museum, providing preliminary findings that enrich our understanding of the application of pigments in Qing dynasty official architecture. These results are expected to be a reference for future research and conservation efforts concerning polychrome paintings.