Oil/water mixtures from industrial and domestic wastewater adversely affect the environment and human beings. In this context, the development of a facile and improved separation method is crucial. Herein, dopamine was used as a bioadhesive to bind tea polyphenol (TP) onto the surface of a polyvinylidene fluoride (PVDF) membrane to form the first hydrophilic polymer network. Sodium periodate (NaIO4) is considered an oxidising agent for triggering self-polymerisation and can be used to introduce hydrophilic groups via surface manipulation to form the second hydrophilic network. In contrast to the individual polydopamine (PDA) and TP/NaIO4 composite coatings for a hydrophobic PVDF microfiltration membrane, a combination of PDA, TP, and NaIO4 has achieved the most facile treatment process for transforming the hydrophobic membrane into the hydrophilic state. The hierarchical superhydrophilic network structure with a simultaneous underwater superoleophobic membrane exhibited excellent performance in separating various oil-in-water emulsions, with a high water flux (1530 L.m−2 h−1.bar) and improved rejection (98%). The water contact angle of the modified membrane was 0° in 1 s. Moreover, the steady polyphenol coating was applied onto the surface, which endowed the membrane with an adequate antifouling and recovery capability and a robust durability against immersion in an acid, alkali, or salt solution. This facile scale-up method depends on in situ plant-inspired chemistry and has remarkable potential for practical applications.