Homologue distributions of alcohol ethoxylates obtained with an unconventional calcium-based catalyst and NaOH as the conventional catalyst are studied in the range of average polyaddition degree from 8 to 15. The fractional compositions of those high molecular weight derivatives of dodecanol and other technical alcohols, Lial 125 and Radianol 1724, are determined as peak area percentages from HPLC chromatograms. Some physico-chemical characteristics of the products as well as by-product contents are also presented. It is shown that the differences in fractional contents between the broad and narrow homologue distributed equivalents remain very significant in that range of higher ethoxylation grades. Consequently, the influence of homologue distributions on some properties of the products can be expected in their practical applications.