The current membrane materials used for oil-water separation suffer from low separation efficiency and poor durability, and membrane contamination is also a key issue that must be addressed urgently. In this paper, a superhydrophilic PANI/Ag/TA@PVDF composite membrane with PANI-Ag NPs heterojunction structure was prepared via chelation and reduction of Ag+ by tannic acid (TA) and in situ growth of hydrochloric acid-doped polyaniline (PANI). TA endows the prepared composite membrane with excellent superhydrophilicity and underwater oleophobicity, remarkable oil-water separation capacity (the separation efficiency of more than 97% for soybean oil), and extraordinary antifouling properties. Notably, the range of photodegradation is expanded from UV to visible light by the construction of a Schottky heterostructure between PANI and Ag NPs, the photocatalytic degradation ability of composite membrane for organic pollutants has been improved obviously, and the degradation efficiency for crystal violet (CV) is 97.9%. Considering these merits, the PANI/Ag/TA@PVDF composite membrane provides an effective strategy to overcome the shortcomings of existing membrane materials, presenting enormous potential in the treatment and purification of oily wastewater.