In this research, ionic liquids (1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide) acted as hierarchically multi-functional materials by empolying not only templates and co-solvents for fabricating shape-controlled nanohybrids but also proton conductors for an electrochemical device. Two ionic liquid-aluminum hydroxide nanohybrids obtaining 1D and 3D shape were synthesized via a one-pot assembled ionothermal process. Humidity played a crucial role in controlling the shape of nanohybrids. The shape-controlled nanohybrids are expected to be a strong candidate for proton conducting materials in terms of reasonable ionic conductivity and thermal stability as a result of the continuous proton conduction channel and nano-confinement.