The main objective of this work was to assess the performance of combined processes, adsorption/ photodegradation of the ciprofloxacin antibiotic (CIP). Adsorption was achieved on natural hydroxyapatite (nat-HA) in the batch mode. The effect of pH (3–12), initial ciprofloxacin concentration (C0, 25–200 mg L−1), adsorbent dose (m, 0.25–3 g L−1), and temperature (T, 298–328 K) on the ciprofloxacin adsorption capacity was studied. At 298 K, the maximum uptake of 147.7 mg g−1 was observed with pH close to 8, 1 g L−1 nat-HA dose, and 150 mg L−1 initial CIP concentration. Adsorption was effective, with a removal percentage of 82% within 90 minutes of contact time. For ciprofloxacin adsorption onto nat-HA, a pseudo-second-order kinetic model is well-suited. The Langmuir isotherm model successfully fit the experimental data and the process was spontaneous and exothermic. The coupling processes (adsorption/photocatalysis) were examined and found to be highly effective. For the remaining concentrations, the maximum degradation efficiency and mineralization yield were ~100% and 98.5%, respectively, for 1 mg L−1 initial CIP. The combination of the strong adsorption capacity of natural hydroxyapatite and the high photocatalytic activity of TiO2 can be an effective technique for removing fluoroquinolone antibiotics from wastewater.