Well-dispersed β-Bi₂O₃/Bi₂O₂CO₃ hollow microspheres were successfully synthesized by calcination an intermediate product fabricated via a solvothermal method using N, N-dimethyl formamide (DMF) as reaction media and carbon nanospheres as sacrifice templates. The molar ratio of β-Bi₂O₃ and Bi₂O₂CO₃ in β-Bi₂O₃/Bi₂O₂CO₃ composites can be adjusted by controlling the roasting conditions, which will influence the utilization of sunlight and the photo-induced charge carrier separation and transfer of the composites constructed, thus affecting photocatalytic activity. Experimental and characterization results suggest that the formation of the special structure could be ascribed to the interdiffusion of BiO⁺ and carbon chain during solvothermal reaction. Control experiments confirmed that as-prepared β-Bi₂O₃/Bi₂O₂CO₃ composites possessed reliable photocatalytic activity and recycle stability for tetracycline degradation, achieving 95.34% under Xe lamp irradiation for 60 min and without significant decrease after four cycles. Our findings provide another insight for the transformation of elemental bismuth into β-Bi₂O₃, and open up a general route for the synthesis of Bi₂O₂CO₃-based composite hollow microspheres for water pollution control.