The morphology-controlled synthesis of nanostructured photocatalysts by an environmentally friendly and low-cost method provides a feasible way to realize practical applications of photocatalysts. Herein, Bi₂WO₆ (BWO) nanophotocatalysts with mulberry shape, sheet-like, and round-cake morphologies have been successfully synthesized through a highly facile solvothermal process by simply adjusting the solvothermal temperature or utilizing selective addition of ethylene glycol as an orientation agent without using strong acids and bases and/or hazardous chemicals. The ratio of ethylene glycol and glacial acetic acid can affect the morphology and oxygen vacancy content of BWO, thereby influencing the photocatalytic performance. The photocatalytic activity of the as-prepared samples was evaluated by degradation of rhodamine B (RhB) and tetracycline under visible-light irradiation. The results indicated that all the BWO samples exhibited morphology-associated photocatalytic activity, and the sheet-like structure of BWO obtained via solvothermal treatment at 120 °C with ethylene glycol and glacial acetic acid ratio of 1:3 achieved the maximum specific surface area and possessed abundant oxygen vacancies, exhibiting outstanding photocatalytic activity for degradation of RhB and tetracycline. The degradation rate of RhB reached 100% within 20 min. To the best of our knowledge, this value is one of the most remarkable values for pristine BWO photocatalysts. Radical capture experiments demonstrated that hydroxyl radicals (·OH) play major roles compared with electrons (e⁻) and holes (h⁺) in the photocatalytic degradation process. A possible mechanism for the photocatalytic degradation of pollutants was proposed to better understand the reaction process. We believe that the more economical, efficient and greener methodology can provide guidance to develop highly efficient photocatalysts with favourable morphology and structure.