In order to reveal the compositions of pigments and adhesives used for polychrome clay sculptures of the Liao Dynasty in Huayan Temple in Datong, we carried out comprehensive analysis of typical polychrome samples. Digital microscopy, scanning electron microscopy-energy dispersive spectrometry (SEM-EDS) and micro-Raman spectrometry were used for pigment analysis. The results show that the red pigments are mainly lead red (Pb₃O₄) and cinnabar (HgS), the green ones mainly malachite [Cu₂CO₃(OH)₂] and atacamite [Cu₂(OH)₃Cl] (these two samples were mixed with two different pigments in similar colors), the blue one is azurite [Cu₃(CO₃)₂(OH)₂], the yellow one orpiment (As₂S₃) and the gold area mainly composed of gold(Au). The composition of adhesives in polychrome samples was detected by Fourier transform infrared (FTIR) spectrometry and thermally assisted hydrolysis and methylation-pyrolysis-gas chromatography/mass spectrometry (THM-Py-GC/MS). The results show that the main adhesives for the gold area are heat-bodied tung oil and glue protein, indicating the existence of the traditional painting technique of “gilding”. For the other color (red, green, blue and yellow) areas, only glue protein is used as adhesives.