The polypropylene/polyethylene (PP/PE) blends with different weight ratio were studied by FTIR spectroscopy. The characteristic absorption bands of PP and PE in different blends were compared. It was found that the ratio of the characteristic absorption peak areas of PP to those of PE is correlated with the weight ratio of PP to PE in the blends. Based on the above results, FTIR mapping technique was applied to characterize the samples prepared by embedding PP fiber into molten PE film, and the distribution of PP and PE in the blends can be obtained from the ratio of the characteristic peak areas of PP to PE. Good agreements have been observed between the IR mapping image and the image obtained using polarized optical microscope. These results indicated that FTIR mapping technique is an effective tool to investigate the phase separation behavior of polymer blends based on the ratio of the characteristic peak areas of different polymers.