Fast proton conduction was achieved in organized lamellar structures with in-plane oriented structure parallel to the substrate surface using a lyotropic liquid crystalline (LC) property. Alkyl sulfonated polyimides (ASPIs) with bent main chain structure were newly synthesized to investigate relations between the higher order structure and proton transport properties. Proton conductivity of all polyimide thin films was greater than 10(-2) S/cm. Grazing incidence small-angle X-ray scattering (GI-SAXS) revealed that both planar and bent ASPI thin films exhibited humidity induced lyotropic lamellar structure. Infrared p-polarized multiple-angle incidence resolution (pMAIR) studies revealed that main chain backbones of both planar and bent ASPI thin films show an in-plane orientation parallel to the substrate surface. Results demonstrate that sulfonated alkyl side chains contribute strongly to the lyotropic LC property, which enhances molecular orderings and proton conductivity by water uptake. This study extends knowledge of the molecular design for highly proton conductive polymers with humidity-induced lyotropic LC property.