A unidirectional water-transfer and wettability gradient compound fibrous film is fabricated by a facile electrospinning technique. One side of the compound film is composite of polyurethane (PU) fibers showing hydrophobicity, and the other side is crosslinked-poly(vinyl alcohol)(c-PVA) fibers exhibiting hydrophilicity. By taking advantages of the hydrophobic-hydrophilic wettability gradient, an interesting unidirectional water-transfer phenomenon has been realized.In brief, water droplet can transfer from the hydrophobic side to hydrophilic side, and spread on hydrophilic side. Additionally, the mechanism of unidirectional water-transfer is proposed.