Abstract Following a new four‐step route, we prepared a family of “extended” glucidoamphiphiles from D ‐glucose, D ‐galactose, and xylitol in which the n ‐dodecyl chain is attached to the glucidic moiety by the linkage Z=O‐Et‐O‐Et‐O‐(α‐PP‐O‐) n′ where‐O‐(α‐PP‐O‐) n is a poly‐(α‐propyloxy) commercial oligomeric mixture (with average length n =6, 10, and 14). This amphiphilic behavior study showed that (i) the glucose derivative exhibits water solubility and hydrophilic‐lipophilic balance values that are close to those found for the glucose compound with Z=‐O‐(α‐PP‐O‐) n (without the Et‐O‐Et group), (ii) all these compounds are more strongly hydrophilic than the corresponding glucidic derivatives with Z=O, (iii) the increase of the poly‐(α‐propyloxy) chain length from ñ =6 to ñ =14 tends to reduce the hydrophilicity slightly.