A La2Ti2O7/acid-modified coal-bearing strata kaolinite (La2Ti2O7/AK) composite was successfully prepared using a simple hydrothermal method. The composite prepared was used in the selective adsorption and photocatalytic degradation system of chlortetracycline hydrochloride (CTC center dot HCl). This system demonstrated the successful preparation of La2Ti2O7/AK, a large amount of active space, and excellent photoelectric properties, which contributed to the adsorption and photocatalytic degradation of CTC center dot HCl by La2Ti2O7/AK. The results demonstrates that the prepared composite has excellent selective adsorption performance for CTC center dot HCl in a single solution at pH = 4 but poor selective adsorption performance for CTC center dot HCl in binary solutions (CTC center dot HCl/TCH and CTC center dot HCl/OTC). Furthermore, the effects of the solution pH, material types, and inorganic ions on CTC center dot HCl adsorption are attributed to the synergistic effect of various adsorption mechanisms. Moreover, the free radical capture and electron paramagnetic resonance (EPR) experiments confirmed that the main free radicals for photocatalytic degradation are center dot O2-, OH, and h(+). Finally, the adsorption and photocatalytic degradation efficiency of La2Ti2O7/AK in case of CTC center dot HCl in wastewater remained at > 70 %. Therefore, its excellent adsorption, unique selectivity, excellent photocatalytic degradation, wide applicability, and outstanding stability in wastewater make it an ideal catalyst for the selective adsorption and photocatalytic degradation of CTC center dot HCl from complex wastewater.