The application and suitability of micro-thermal analysis to detect changes in the chemical and physical properties of coating due to ageing and especially photo-degradation is demonstrated using a model polyester coating based on neopentyl glycol isophthalic acid. The changes in chemical structure like chain scission and cross-linking are manifested by a shift of the LTA detectable T-g and by a change of the slope of the part of the LTA graph responsible for the penetration of the hot sensor into the material after passing the glass transition temperature. As such LTA is a valuable tool to have a quick look into coating surfaces and especially their ageing. The photo-degradation of polyester in air leads to the formation of a cross-linked network at a surface layer of about 3-4 mu m coupled with an increase in hardness and of the glass transition temperature by similar to 90 K, the effect is less drastic for a photo-degradation in a nitrogen environment. Moreover, the presence of a non-equilibrium dense surface layer with a higher T-g formed during the drying of the coating formulation and the film solidification can be shown. (C) 2010 Elsevier B.V. All rights reserved.