Photo- and thermal ageing of nitrile butadiene rubber (NBR)/poly(vinyl chloride) (PVC) blends cured with sulfur and a vulcanization agent have been studied. Characterization of the aged NBR/PVC films was performed by using FTIR and UV‒visible spectroscopy, DMTA, Shore A hardness and swelling measurements. The objective was to understand the formation of cracks upon ageing and to put in evidence correlations between the different scales: from chemical structure to functional properties.