Assignments of nearly all the 1H chemical shifts of glycogen are made by 2-D 1H-1H homonuclear and 13C-1H heteronuclear COSY. We demonstrated that it is possible to obtain well-resolved 2-D n.m.r. spectra for a large molecule like glycogen. The seven nonequivalent protons of the glucose residues in the alpha-(1----4)-linked chains, and of those at the nonreducing ends, were completely assigned. Distinct chemical shifts for H-1 and H-2 immediately adjacent to the alpha-(1----6) bonds at the branch points were also determined. Several modifications of previous 13C chemical shift assignments were made from the heteronuclear 2-D n.m.r. data.