Vibrational Spectroscopy can provide molecular vibrational information and can be very sensitive to the conformation of polymer molecule chains and interaction between chains. Vibrational Spectroscopy Imaging as an in situ non-damage detection is widely applied to the study of polymer blend’s properties such as crystallization, distribution of phase state and interface diffusion. The present paper emphasized to summarize the headway of application research of polymer blend by imaging techniques of Raman Spectroscopy and Infrared Spectroscopy and their derivative techniques with high-space resolution ratio, such as the combination of Infrared Spectroscopy and atomic force microscope (IR-AFM), the combination of Raman Spectroscopy and Atomic Force Microscope (Raman-AFM) and Tip-Enhanced Raman Spectroscopy (TERS), aiming to explore and expand the application of vibrational spectroscopy imaging techniques in the polymer field.