The bonding properties of PVA thin films are explored as a function of annealing in pure and Rhodamine B doped self-standing films. X-ray photoelectron spectroscopy measurements have shown high quality, impurity free films, where the bonding is found between C and O elements in agreement with the standard data of polymers. Upon annealing, the bonds break and signals come only from elemental carbon and oxygen at their respective binding energy positions. The experiments are able to show that upon annealing at 65°C, all the bonds break and hence electronic properties are completely modified.