Rice is the most widely consumed staple food, and is cultivated worldwide to satisfy our daily caloric needs. Thus, extensive efforts on rice breeding and biotechnology have substantially focused on the development of elite cultivars with high yields and better grain quality, as well as enhanced resistance against biotic and abiotic stresses. Recently, it has been observed that rice is more than a just grain-producing crop. Carbon-rich materials of the rice cell wall polysaccharides from post-harvest wastes, including the straw and husk, have been converted into bioethanol and other invaluable, renewable materials. In order to maximize the utilization of cell wall-derived resources, it is imperative to understand cell wall chemistry and molecular mechanism underlying cell wall biosynthesis in rice. In the last decade, several approaches, including mutational genetics and the functional characterization of candidate genes, have been successful in isolating some of cell wall biosynthetic genes in rice, marking the first step forward in obtaining a complete understanding of rice cell wall biosynthesis, although the exact biochemical functions have not been conclusive. In this paper, we focus on integrating old and new information to provide an updated perspective in the cell wall formation of rice, highlighting the chemical structures and biosynthesis of rice cell wall polysaccharides.