Poly(l‐lactide) (PLLA)/TiO2 composite membranes were fabricated by immersion precipitation method. The resulting membranes were characterized using various methods including XRD, ATR‐FTIR, TGA, DSC, SEM, goniometer, and molecular weight cut‐off. The antifouling performance of the membrane was investigated through the filtration experiments of the oil/water emulsion. XRD, SEM, and ATR‐FTIR results indicated that TiO2 was successfully introduced into the membrane, while DSC and TGA indicated the enhancement of thermal stability of membrane. The improvement of membrane hydrophilicity was confirmed by goniometer. In addition, the pore size and porosity on the membrane surface varied obviously with increasing the TiO2 loading. It was concluded that PLLA/TiO2 composite membranes had better antifouling and recycling performance compared with the pure PLLA membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43542.