Unidirectional and long-distance liquid transport is critically important to a range of practical applications, e.g., water harvesting, microfluidics, and chemical reactions. Great efforts have been made on liquid manipulation; most of which, however, are limited in the air environment. It is still a great challenge to achieve unidirectional and long-distance oil transport in an aqueous environment. Herein, we have successfully fabricated an underwater superoleophilic two-dimensional surface (USTS) with asymmetric oleophobic barriers to arbitrarily manipulate oil in aqueous medium. The behavior of oil on USTS was carefully investigated, of which the unidirectional spreading capability was originated from the anisotropic spreading resistance resulted from the asymmetric oleophobic barriers. Accordingly, an underwater oil/water separation device has been developed, which can achieve continuous and efficient oil/water separation and further prevent the secondary pollution caused by oil volatilization.