A membrane with superamphiphilicity presents many advantages in various oil/water separation applications due to its switchable wettability by prewetting. However, it is still a great challenge to switch between two types of superwettability on a single cellulose surface by switching between different liquid media. Herein, in order to obtain in-air superamphiphilic and under-liquid dual superlyophobic membranes, dopamine-modified nitrocellulose membranes (with a pore size of 0.22 μm) were prepared via a facile immersion modification approach. Under 0.08 MPa, the as-prepared NC membrane switches wettability by prewetting to achieve on-demand oil/water separation, and the separation efficiency is more than 99.9%. Futhermore, the membrane prepared in this work can also be applied to high-efficiency on-demand separation of surfactant-stabilized emulsions with a separation efficiency greater than 99.0%. Hence, the PDA-modified NC membrane is a promising controllable oil/water separation material in terms of repeatable cycles, separation efficiency, flux, prominent long-term durability and anti-oil fouling.