Optical and magnetic responsive deforming multilayered films with rapid deforming recovery property were successfully fabricated by electrospinning technology. Polyvinyl alcohol (PVA)/liquid crystal (LC) 5CB (4‐cyano‐4'pentylbiphenyl)/graphite fiber film was orderly collected on the thermoplastic polyurethanes (TPU) substrate film by parallel electrode electrospinning method. Graphite and nano‐magnetic particles had been added to endue it with optical and magnetic responsibility. Evaluated by a customized 3D‐printed platform, the deforming multilayered film shows its high deforming recovery speed. Therefore, the proposed deforming multilayered films can be applied in the field of bionic control with the advantage of rapid optical and magnetic responsibility, nontoxicity, and simple fabrication approach. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46884.