A new class of small molecule-based amphiphilic carbazole-containing compounds has been designed and synthesized. Detailed analysis of the temperature- and solvent-dependent UV-vis absorption spectra has provided insights into the cooperative self-assembly mechanism of the carbazole-containing compounds. Interestingly, the prepared amphiphilic rigid–soft compounds were also found to display a lower critical solution temperature (LCST) behavior in aqueous solution, which is relatively less explored in small molecule-based materials, leading to promising candidates for the design of a new class of thermo-responsive materials.