Agarose/succinoglycan hydrogels were prepared as pH-responsive drug delivery systems with significantly improved flexibility, thermostability, and porosity compared to agarose gels alone. Agarose/succinoglycan hydrogels were made using agarose and succinoglycan, a polysaccharide directly isolated from Sinorhizobium meliloti. Mechanical and physical properties of agarose/succinoglycan hydrogels were investigated using various instrumental methods such as rheological measurements, attenuated total reflection–Fourier transform infrared (ATR-FTIR) spectroscopic analysis, X-ray diffraction (XRD), and field-emission scanning electron microscopy (FE-SEM). The results showed that the agarose/succinoglycan hydrogels became flexible and stable network gels with an improved swelling pattern in basic solution compared to the hard and brittle agarose gel alone. In addition, these hydrogels showed a pH-responsive delivery of ciprofloxacin (CPFX), with a cumulative release of ~41% within 35 h at pH 1.2 and complete release at pH 7.4. Agarose/succinoglycan hydrogels also proved to be non-toxic as a result of the cell cytotoxicity test, suggesting that these hydrogels would be a potential natural biomaterial for biomedical applications such as various drug delivery system and cell culture scaffolds.