The alpha/beta-Bi2O3 photocatalyst was successfully synthesized by a novel solvothermal-calcination method. The physical and chemical properties of as-prepared samples were characterized based on XRD, XPS, SEM, TEM, EDS, BET, UV-vis DRS and PL techniques. The synthesized alpha/beta-Bi2O3 photocatalyst exhibited enhanced photocatalytic activity for 17 alpha-ethinylestradiol (EE2), and 96.9% of EE2 was degraded after only 24 min of visible-light irradiation using alpha/beta-Bi2O3 as photocatalyst. The reaction rate constant over alpha/beta-Bi2O3 photo catalyst was 1.42, 2.23, 9.22 and 54.1 times higher than pure beta-Bi2O3, alpha-Bi2O3+beta-Bi2O3, alpha-Bi2O3 and P25 respectively. Effect of catalyst dosage and pH value was investigated. The possible photocatalytic mechanism has been discussed on the basis of the theoretical calculation and the experimental results. alpha/beta-Bi2O3 was a fairly stable and efficient photocatalyst under the studied experimental conditions, proving that the alpha/beta-Bi2O3 photocatalyst was a promising photocatalyst for the practical application.