Heterojunction was mainly used to realize the separation of charge carrier in current studies, but it did not bring about any other effect. In this paper, Bi2Sn2O7 was introduced into α-Bi2O3 to construct a direct Z-type Bi2Sn2O7/α-Bi2O3 heterojunction. It not only accelerated the rapid separation of electrons and holes, but also induced a huge redshift of absorption edge to enlarge the visible light absorption range. Such result led into the optimal sample being able to degrade 95% of norfloxacin and 92% of bisphenol AF for 90min of visible light irradiation. Under the same testing conditions, the removal efficiency of these two pollutants in the drinking water also attained 94% and 90% to demonstrate a good application. Moreover, the cycling test results indicated that the Bi2Sn2O7/α-Bi2O3 could be sustainably utilized. The electrons, holes, superoxide radical (•O2-) and hydroxyl radical (•OH) were the active substances in the process of degradation. The numbers of the Escherichia coli were 0.69×106 CFU/mL and 0.75×106 CFU/mL in the solutions after degradation to denote non-toxicity of the final products. Thus the Bi2Sn2O7/α-Bi2O3 composite could be applied in purification of various waste waters.