In summary, a facile and generic approach for high proton conductivity is developed by incorporating nanotubes bearing sulfonate polyelectrolyte brushes into basic polymer. Halloysite nanotubes are modified via distillation–precipitation polymerization to graft sulfonate polyelectrolyte brushes and then embedded into CS matrix to prepare nanohybrid membranes. The physicochemical and proton conduction properties of nanohybrid membranes are extensivelyinvestigated, and it is found that SHNTs play at least three roles for enhancing the conductivity of CS matrix: (i) generating acid–base pairs (–S–O3þH–2HN–) at SHNT–CS interface,whichworkaslow-barrierproton-hopingsites;(2)creating continuous pathways along the nanotubes due to their high aspect ratios; and (3) inserting into CS chains and then forming wider pathways with the aid of the long brushes on SHNTs. In such way, SHNTs promote the Grotthuss-type transfer of CS membrane in an efficient way. Additionally, the strong attractive interactions from SHNTs suppress the chain motion of CS, conferring improved thermal and mechanical stabilities as well as methanol barrier property on the nanohybrid membranes. Incorporating the versatile filler with hierarchical, tunable brushed-structure into polymeric or inorganic materials bulk may offer a promising strategy to pursue highly conductive devices for diverse energy and environment relevant fields.