To achieve the green, sustainable, and controllable recovery of oil-water resources and to address the limited functionality of single superwet materials in oil-water separation, this study reports a multifunctional oil-water separation strategy by compositing the underwater superoleophobic and underoil superhydrophobic materials (HS). The underwater superoleophobic quartz sands with an oil contact angle of 152.68° were prepared by adjusting the particle size. This material demonstrated a water flux of 4688 L m-2 h-1 and a low-density oil and water mixture separation efficiency of 98.6%, which remained above 97.9% over 50 cycles. It was effective in separating oil-in-water emulsions with a separation efficiency of >99%. For HS, quartz sands were modified with dodecyltrimethoxysilane. The optimized HS-4 exhibited superhydrophobic properties with a water contact angle of 157.06°. It achieved an oil flux of 5775 L m-2 h-1 and a water and dichloromethane mixture separation efficiency of 98.4%. Additionally, they exhibited significant potential in the separation of water-in-oil emulsions. Furthermore, by placing the underwater superoleophobic and underoil superhydrophobic units at the bottom of the filter, we achieved cyclic separation of high-density oil and water mixtures, low-density oil and water mixtures, water-in-oil emulsions, and oil-in-water emulsions. The separation efficiency consistently exceeded 96.5% over 10 cycles. In addition, the oil-water separation mechanism of underwater oleophobic and underoil hydrophobic materials was demonstrated by the relative concentration distribution of water and oil with molecular dynamics simulations. This intelligent oil-water separation method marks a significant advancement in the sustainable separation of diverse oil-water mixtures.