The use of Polyvinylidene fluoride (PVDF) membranes is constrained in wastewater treatment because of their hydrophobic nature. Therefore, a large number of researchers have been working on the hydrophilic modification of their surfaces. In this work, a superhydrophilic tea polyphenols/silica composite coating was developed by a one-step process. The composite coating can achieve not only superhydrophilic modification of the surface, but also the inner surface of the porous PVDF membrane, which endows the modified membrane with excellent water permeability. The modified membrane possesses ultrahigh water flux (15,353 L·m−2·h−1). Besides this, the modified membrane can realize a highly efficient separation of oil/water emulsions (above 96%).