The gelation and crystallization behavior of a biological surfactant, sodium deoxycholate (NaDC), mixed with L-taric acid (L-TA) in water is described in detail. With the variation of molar ratio of L-TA to NaDC (r = n(L-TA)/n(NaDC)) and total concentration of the mixtures, the transition from sol to gel was observed. SEM images showed that the density of nanofibers gradually increases over the sol-gel transition. The microstructures of the hydrogels are three-dimensional networks of densely packed nanofibers with lengths extending to several micrometers. One week after preparation, regular crystallized nanospheres formed along the length of the nanofibers, and it was typical among the transparent hydrogels induced by organic acids with pK(al) value <3.4. Small-angle X-ray diffraction demonstrated differences in the molecular packing between transparent and turbid gels, indicating a variable hydrogen bond mode between NaDC molecules.