In this study, a new polymorph of ciprofloxacin saccharinate has been thoroughly evaluated with respect to structural as well as biopharmaceutical properties. Preliminary characterization of the new polymorph was performed by differential scanning calorimetry and thermogravimetric analysis, later confirmed by Fourier transform infra-red spectroscopy. The crystal structure was determined from the powder X-ray diffraction pattern using the direct-space algorithm. It lies in the triclinic P-1 space group. It is having lattice parameters different from previously reported forms. The solid-state 13C NMR data calculated from the crystal structure by exploiting density functional theory were found to be in excellent agreement with corresponding experimental 13C NMR data, thus providing a robust validation of the authenticity of the structure. The prepared polymorph shows enhanced aqueous solubility and dissolution rate in contrast to previously reported polymorph. The new form demonstrated improved oral bioavailability and inhibition of bacterial species. The enhanced biopharmaceutical properties are attributed to the higher extent of its absorption and distribution with respect to the individual components. The new form is a potential candidate for the pharmaceutical industry.