The C-H/pi interactions as the key driving force for the construction of supramolecular gels remain a great challenge because of their weak nature. We hereby employed for the first time weak C-H/pi interactions for the construction of supramolecular dendritic gels based on peripherally methyl-functionalized poly(benzyl ether) dendrimers. Their gelation property is highly dependent on the nature of the peripheral methyl groups. Furthermore, single-crystal X-ray analysis and NMR spectroscopy revealed that multiple C-H/pi interactions between the proton of the methyl group and the electron-rich :peripheral methyl-substituted aryl ring played significant roles in the formation of supramolecular nanofibers and organogels. This study uncovers the critical role of weak noncovent interactions and provides new insights into the further design of self-assembled nanomaterials.