Infrared microscopic imaging techniques with an aid of augmented alternative least-squares (ALS) regression analysis have been employed for analyzing the interface structure involved in two wrapping films that have a common layered structure with different adhesive intermixing between the adjacent layers. A conventional single-band mapping technique exhibited a problem that the imaging results responded to the selection of an analytical band. On the other hand, the augmented ALS technique has proved to powerfully decompose the collection of spectra into spectroscopically independent spectra and quantity variations in the mapping area. Regardless, the chemometric analysis could not commonly be applied to the two films, and different pretreatments were necessary for analysis of the two films. As a result, the concentration profiles across the boundaries have readily revealed that the two films have largely different adhesive structures. In addition, the structural difference was found to be a reason an identical analytical technique cannot be employed for analysis of the two films. This study shows an appropriate pretreatment and selection of a chemometric technique considering the samples that have different spectroscopic characters are of great importance for effectively draw map images and pure-component spectra of the constituents.