The synthesis of a series of propeller-shaped hexaphenylbenzenes (HPB) substituted with one (3), two (1) and four (2) poly(ethylene glycol) (PEG) chains as well as of an ortho-connected trimer of HPBs bearing two PEG chains (4) result in remarkable amphiphiles with supramolecular organization and suppressed dynamics. The thermodynamic state and self-assembly are studied with DSC and X-ray diffraction whereas the dynamics of HPB core and PEG segments are elucidated via heteronuclear NMR and dielectric spectroscopy. The phase state is largely determined by the rod-coil nature and architecture of block copolymers comprising a HPB "mesogen' and flexible PEG chains. In addition, the molecular shape of the ortho-connected trimer of HPBs (4) promotes pi-pi stacking and gives rise to a supramolecular columnar organization uncommon to most other HPBs. The emerging dynamic picture is that of practically frozen HPB cores that are surrounded by mobile PEG segments. The implications of this supramolecular organization-stacked/immobile HPB cores and flexible/fast moving PEG segments with suppressed crystallinity to ion transport are discussed with respect to the conductivity measurements in amphiphiles doped with LiCF3SO3 salt at different [EG]: [Li+] ratios. A unique feature of the doped amphiphiles is the Vogel-Fulcher-Tammann temperature dependence of ionic conductivity with values that are comparable to the archetypal polymer electrolyte (PEG)(x)LiCF3SO3.