Cell wall (CW) plays an important role in Cd accumulation in roots of metal-tolerant plants, including rice. The role of CW polysaccharides, especially pectin, in binding Cd in roots of a high Cd accumulating (HA) rice line of Lu527-8 and a non-high Cd accumulating (NHA) rice line of Lu527-4 was investigated in this study. About 59%-63% of Cd in roots of the two rice lines was bound to CWs, indicating that CW was the main site for Cd accumulation in roots of the two rice lines. Cd adsorbed on the root CWs of the HA was 1.1-1.2 times more than that of the NHA, demonstrating the root CWs of the HA showed greater Cd binding ability. Cd exposure induced more Cd accumulation in pectin and hemicellulose in the HA. In particular, up to 65% of Cd accumulation in root CWs of the HA was observed in pectin. The removal of pectin lead to a 50% decrease for the amounts of Cd adsorption on root CWs of the HA, indicating that pectin was the major binding site for Cd in root CWs of the HA. The HA showed greater pectin methylesterase activities, resulting in lower degree of pectin methylesterification along with more low-methylesterified pectins in root CWs than the NHA. The more accumulation of low-methylesterified pectins in CWs induced by Cd contributed greatly to the high Cd accumulation in roots of the HA rice line of Lu527-8.