• Series of Bi 0 /OVs-BiOCOOH photocatalysts with hollow structure were successfully designed and constructed. • The structure–activity relationship between catalyst structure and properties were elucidated. • A possible formation mechanism for the special structure was proposed. • The heterojunctions present excellent activity and stability for photocatalytic TC removal efficiency. Herein, we prepared visible light responsive well-dispersed Bi 0 /OVs-BiOCOOH hollow microspheres through solvothermal method employing colloid carbon nanospheres (CSs) as sacrificial template and reductant. The characterization results show that CSs play multiple roles in the synthesis of hollow Bi 0 /OVs-BiOCOOH microspheres, in which the hollow structure may be caused by the redox reaction of CSs and BiO + during synthesis. The SPR effect of Bi 0 can enrich the photocatalytic performance by promoting the absorption of visible light. Furthermore, a defective energy level can be established by introduction of oxygen vacancies (OVs) on the surface of BiOCOOH, improving photocatalytic capability by accelerating the separation of photogenerated carriers. The degradation performance of Bi 0 /OVs-BiOCOOH for decontamination of tetracycline (TC) is 4.86 times than that of BiOCOOH. Based on the observations, the underlying photocatalytic mechanism of Bi 0 /OVs-BiOCOOH for photodegradation of TC was elaborated.