The effect of the generation number on sorption behavior of the liquid crystalline (LC) poly(propyleneimine)dendrimers G1-G4 terminated with n-hexadecyl groups has been studied by inverse gas chromatography. To examine the accessibility of the terminal-group shell by small molecules, methyl-substituted derivatives of benzene, pyridine, aniline, and naphthalene have been chosen as probe solutes. The retention volumes and activity coefficients of the solutes are not linearly related to the generation number. The highest thermodynamic solute-solvent compatibility is observed for the dendrimer G2. On the other hand, the highest structural selectivity is observed for the dendrimer G3. The said sorption features are rationalized in terms of local ordering and a higher degree of tightness of the terminal-group shell in the macromolecules of high generations.