Different kinds of bread, stored at constant temperature and at controlled humidity conditions for a week since their manufacturing date, were analysed by Attenuated Total Reflectance‐Fourier Transform InfraRed (ATR‐FTIR) spectroscopy. The collected spectra were processed by Principal Component Analysis (PCA), in order to evaluate the changes occurring during bread ageing. For the sake of comparison, the 1060‐950 cm−1‐1 spectral window has been also investigated by curve‐fitting methods. It was observed that the first PC increases monotonically with ageing of samples. Furthermore, the more influential variables on PC1 correspond to spectral regions where are located stretching and bending bands, which are mainly attributed to typical starch bonds vibrations.