A mixture of a cholic acid dimer with a secondary amine group and formic acid at a molar ratio of 1/1 is regarded as an organic salt, and it self-assembles in aqueous solutions to form monodisperse nanofibers. The nanofibers are separated at low concentrations of the mixture but entangle with each other at high concentrations to form well-dispersed and randomly arranged 3D fibrous networks. Above the minimum gelation concentration of the dimer, the fibrous network is strong enough to gelate the aqueous solutions to form a hydrogel. Hydrogels obtained from the dimer salt at a lower concentration are isotropic and show extinction between crossed polarizers in the polarizing microscope, whereas they become anisotropic (i.e., nematic hydrogels) upon increasing the dimer salt concentration or under physical stirring. The parallel arrangement of nanofibers from randomly directed fibrous networks may be responsible for the formation of such nematic hydrogels.