Photochemical degradation of commercial polyvinyl acetate (PVAc) homopolymer and PVAc paints mixed with burnt umber, cobalt blue, cadmium red dark, nickel azo yellow and titanium white commonly used for artworks were studied by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR). Py-GC/MS with single-shot technique was used for the characterization of the thermal degradation of PVAc at different temperatures, while the double-shot technique of Py-GC/MS was used to reveal the differences in the specimens before and after UV ageing, including the changes of detectable amounts of deacetylation product - acetic acid and plasticizers such as diethyl phthalate (DEP). Furthermore, the relative concentration of the pyrolysis products of the paint samples could be measured and compared in the second step of the double-shot Py-GC/MS, which are highly dependent on the presence of pigments and the ageing status of PVAc paints.