Among the innovative materials used by 20th-century artists, polyurethane (PUR) has been shown to be highly unstable, and therefore artworks made of it are now in need of careful conservation strategies. This study presents a multi-analytical investigation of PUR foam scenic objects originally made between the 1960s and 1970s during the Italian Arte Viva movement. The main components in the foam and additives were characterized through micro attenuated total reflectance infrared spectroscopy (μ-ATR-FTIR) and pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS). Painted samples were further investigated through μ-FTIR and Raman spectroscopy to define binders and pigments. The use of μ-ATR-FTIR in combination with evolved gas analysis-mass spectrometry (EGA-MS) allowed the variable conditions of the artworks to be assessed and attained some insights into the chemical processes responsible for aging. At the same time, morphological changes due to the degradation phenomena were recorded through optical (OM) and scanning electron microscopy (SEM). The detailed characterization of the PUR foam and painting materials was helpful in attaining some insights into harmful environmental parameters for the artworks, thus informing preventive conservation.