Sb-doped SnO₂ electrodes were prepared with the practical sol–gel method and were used for the electrocatalytic degradation of ciprofloxacin (CIP) in aqueous solution. Results from the electrochemical characterization (including cyclic voltammetry, linear sweep voltammetry, and electrochemical impedance spectroscopy) showed that the electrode with 16 coating times (SSO-16) had the highest oxygen evolution potential of 2.2 V (vs. SCE) and the highest electrochemically active area of 3.74 cm². The results of scanning electron microscopy and X-ray diffraction showed that the coating times could affect the surface morphology and crystal structure of the electrodes, and the SSO-16 electrode had a denser surface, higher crystallinity, and smaller grain size (28.6 nm). Moreover, the experimental parameters for CIP degradation with SSO-16 were optimized, and the removal ratio of CIP reached to almost 100% within 60 min. In addition, the possible degradation pathways of CIP were proposed. And the stability and reusability of the SSO-16 electrode were also studied. These results are valuable for the preparation of high electrocatalytic performance electrodes by a sol–gel coating method for electrochemical degradation of antibiotics.