The thermally induced structural changes of 6FDA-ODA PAA films in the presence and absence of a base catalyst, 2,6-dimethyl piperidine, were investigated using in situ FTIR spectroscopy. In addition, principal component analysis (PCA) and 2D correlation spectroscopy (2D-COS) were applied to clarify the thermal imidization behaviors. Based on the PCA results, we can confirm the various products formed during thermal imidization. The results of 2D correlation analysis revealed the thermally induced changes in the spectra of the 6FDA-ODA PAA films. In addition, we propose that the thermal imidization of the 6FDA-ODA PAA film in the presence of a base catalyst, 2,6-diemthyl piperidine, starts at a lower temperature than it does in the absence of a base catalyst.