An interesting "water diode" film is fabricated by a facile electrospinning technique. The fibrous film is a composite of hydrophobic polyurethane (PU) and hydrophilic crosslinked poly (vinyl alcohol) (c-PVA) fibrous layers. By taking advantages of the hydrophobic–hydrophilic wettability difference, water can penetrate from the hydrophobic side, but be blocked on the hydrophilic side.