Abstract Herein, we report on a supramolecular TX-100-based molecular gel, which self assembles largely due to hydrophobic interactions, and we clearly distinguish between surface versus bulk gelation mechanism. The phase diagram of these salt-free solutions, and their gels were characterized by dynamic light scattering (DLS), viscometry, rheology, and surface tension methods to map their microstructure, and thermo-viscoelastic properties. We demonstrate the spontaneous evolution of several hierarchical, but self-assembled soft matter phases starting from a homogeneous aqueous solution as it was gradually cooled from 60 °C to room temperature (20 °C). The Cole-Cole plot profile (loss versus storage modulus plot) indicated that this suspension produced the following three phases: (i) for [TX-100] 60% (v/v), heterogeneous melt. The system exhibited a clear UCST separating the sol and gel domains, and the proposed phase diagram embodied all the observed phases. The gelation time, and the free-energy of gelation were determined from surface tension, and viscosity measurements, they revealed that the self-assembly, and network formation at the air-liquid interface occurred at least 200 s later than the bulk, a behaviour that was anomalous. The gelation phenomenon was discussed through homogeneous nucleation and growth model where the interfacial surface and volume free-energy governed the gelation kinetics. The gel state was dominated by structured water (characterized by Raman band at 3200 cm−1), whereas both in the solution, and in the melt phase there was propensity of partially structured water. It was concluded that aqueous TX-100 dispersions can yield a variety of soft matter phases rich in hierarchy, and dynamics, much of which is not probed hitherto.