Three HECs with a high MS (HEC 1: 1.89, HEC 2: 1.94, HEC 3: 3.03) were analyzed with respect to their substituent distribution and tandem reaction in the glucosyl unit by GLC of the corresponding glucitol acetates, and along the polymer chain by MALDI-ToF-MS after a multi-step sample preparation. For comparison of the experimental data with a random pattern an extended Bernoulli plot was applied to calculate a random distribution for the composition of un-, mono-, di-, tri-, and up to heptasubstituted glucosyl units (c0, c1, c2, ... c7).