The role of peripheral groups (PGs) on dendrimers in the spontaneous higher-level organization of hierarchically assembled nanofibers was investigated in a series of POSS-based dendritic gelators (POSS-Lys-X, X: -Boc, -Cbz, -Fmoc, etc.). We demonstrate that the PGs not only affect the gelation ability in solutions, but also the construction of orderly entangled fibrous supramolecular networks, e.g., "loofah-like" networks. Attributed to the PGs (especially the -Boc group) causing a lower cooperative assembly, the steady state with the lowest potential energy of gelators can be easily achieved by the higher ordering of nanofiber entanglement into superstructures. The -Boc group-containing dendrimers show low molar enthalpy and molar entropy of gelation, which help the construction of unique three-dimensional (3D) "loofah-like" superstructures. In contrast, the high cooperative assembly of the dendrimer (-Cbz as the PG) promotes the gelator into a higher enthalpy gelation process, with a constructed normal fibrous network. Hence, the PGs of POSS-based dendrimers act as the crucial factor in controlling the hierarchical self-assembly via a thermodynamics approach. This research presents new perspectives to explicate the relationships between PGs of dendrimers, supra-architectures and gel performances, which further guide the design of functional supramolecular materials via controllable self-assembly.