The NIR/MIR micro-imaging can supply not only the information of spectra, but also the information of spacial distribution of the sample, which is superior to the traditional NIR/MIR spectroscopy analysis. In the present paper, polyethylene and parafilm, with similar appearances, were regarded as the research objects, of which the NIR/MIR micro-imaging was collected. Chemical imaging (CI) and compare correlation imaging were carried out for the two materials respectively to discuss the imaging methods of the two materials. The result indicated that the differentiation of the CI values of the two materials in the NIR/MIR CI for material Ⅱ was 0.004 8 and 0.254 8 respectively, while those in the NIR/MIR CI for material Ⅰ were 0.002 6 and 0.326 5, respectively. Clear CI was acquired, and the two materials could be differentiated. The result of the compare correlation imagings indicated that the compare correlation imagings, in which the NIR/MIR spectra of the two materials were regarded as reference spectra respectively, can differentiate the two materials remarkably with clear imagings. In the compare correlation imagings of MIR micro-imaging, the difference of the correlation coefficients between the two materials’ MIR spectra and the reference spectrum was more than 0.12, which showed a better imaging result; while a tiny difference of the correlation coefficients between the two materials’ NIR spectra and the reference spectrum could be employed to show a clear imaging result for NIR compare correlation imaging so as to differentiate the two materials. This thesis, to some extent, can supply the reference to not only the rapid discrimination of the safety of the packaging material for agri-food, but also the imaging methods for NIR/MIR micro-imaging to differentiate the different materials.