Due to the deficiency of energy supply and negative environmental impacts. Much attentions have been paid to agnicultural these lignocellulosic the replacement of fossil resources with and forestry biomass for the production of bio-fuels, chemicals and biomaterials on a global scale. Highly effective utilization of biomass is dependent on full understanding of their chemical composition and structural characteristics. A state-of-the-art Raman spectroscopy has evolved an important and nondestructive technique for plant research as information concerning histochemistry and structural characteristics of plant cell walls can be investigated in a nearly native state. In this paper, the principle of Raman imaging was introduced briefly. Meanwhile, the research progress in structural analysis of major components, micro-area distribution and molecular organization of the cellulose and lignin in the plant cell walls by Raman spectroscopy was summarized. The aim of the review is to promote the application of Raman spectroscopy to the study of plant cell walls.