Hydrogels are important soft materials with intriguing properties. By taking advantage of the host–guest interactions and multiple molecular interactions, it is expected that novel hydrogel systems can be formed. This strategy has been implemented here, transparent hydrogels were formed by using a newly-synthesized anionic surfactant, sodium 2-(4-phenylphenoxy)dodecanoate (C₁₂biphNa), and β-cyclodextrin (β-CD) in different proportions and their properties were investigated. Gelation of water occurs at extremely low surfactant concentrations (5 mM for a 1 : 3 C₁₂biphNa : β-CD system), and a single C₁₂biphNa with its associated β-CDs can trap about 11 000 water molecules on average. In addition, the systems are fragile to mechanical stimulus and thus show mechanical sensitivity. Cryo-TEM reveals that the hydrogels have a microstructure consisting of rigid nanowire-like aggregates (with cross-sectional diameters of about 7–8 nm) locally distributed in a parallel manner in solution. These microstructural features are responsible for the peculiar properties of the hydrogel systems presented. The inclusion complexes formed by C₁₂biphNa and β-CD were investigated using ¹H NMR and 2D nuclear overhauser effect spectroscopy and their aggregation state was proposed. This work enriches the connotation of nonamphiphilic self-assembly and provides inspiration for constructing new functional soft materials.