Superwettable multifunctional materials with stimuli-responsive have become increasingly attracted broad attention and been studied in oil-water separation fifield in recent years. However, it still remains big challenging to fabricate smart materials from the point of view of the complexity and environmental green. Herein, a simple and environmentally friendly strategy for preparing superwettable materials with pH-responsive has been proposed. The smart fabric that can be reversibly switched between superhydrophobicity-superoleophilicity and superhydrophilicity-underwater superoleophobicity according to difffferent pH solutions, which is obtained by monomer polymerization. In view of this ingenious mechanism, it can separate various oil-water mixtures by gravity-driven with excellent separation effiffifficiency and flflux. More importantly, the complicated oil/water/oil mixtures can be rapidly in situ separated without pretreatment. Moreover, it is amazing that the resulted fabric is able to separate two organics by chemical reaction, which has rarely been reported in the previous literature, proving a new idea for the separation of organics. And it also exhibits brilliant durability and chemical stability under severe conditions. Simultaneously, it overcomes the secondary environmental pollution of traditional flfluorochemicals. Based on all the advantages mentioned above, the resultant fabric will play a more extensive and substantial role in the fifield of oil-water separation and industrial operation.