This work describes the gelation behaviors of a biological amphiphile, deoxycholate (DC-), in aqueous solution by adding inorganic salts and modulating pH. Electrostatic interaction and hydrogen bonding can separately act as the controlling interaction for the hydrogel formation. The hydrogels formed at higher pH (about 8.5) through introducing monovalent inorganic cations (Na+) are mainly driven by electrostatic interaction between deoxycholate species and Na+ ions. When pH is decreased, with the formation of DCA molecules, hydrogen bonding between DC- and DCA come into being another leading role to construct the hydrogels, which can induce the gels within an appropriate pH region (6.7-7.3) without inorganic cations. Gels constructed through the self-assembly of deoxycholate present diverse properties according to the difference in the main driving force. Moreover, the combination of the two important interactions can significantly enhance the gelation ability.