A series of amphiphilic dendrons n-18 (n: generation number, 18: octadecyl chain) based on an aliphatic polyether denderitic core and octadecyl peripheries were synthesized using a convergent dendron synthesis consisting of a Williamson etherification and hydroboration/oxidation reactions. This study investigated their thermal and self-assembling behavior in the solid state using differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR) absorption spectroscopy, and small angle X-ray scattering (SAXS). DSC indicated that the melting transition and the corresponding heat of the fusion of the octadecyl chain decreased with each generation. FT-IR showed that the hydroxyl focal groups were hydrogen-bonded with one another in the solid state. DSC and FT-IR indicated microphase-separation between the hydrophilic dendritic cores and hydrophobic octadecyl peripheries. SAXS data analysis in the solid state suggested that the lower-generation dendrons 1-18 and 2-18 self-assemble into lamellar structures based upon a bilayered packing of octadecyl peripheries. In contrast, the analyzed data of higher-generation dendron 3-18 is consistent with 2-D oblique columnar structures, which presumably consist of elliptical cross sections. The data obtained could be rationalized by microphase-separation between the hydrophilic dendritic core and hydrophobic octadecyl peripheries, and the degree of interfacial curvature associated with dendron generation.