Magnetic nanofiller is helpful for improving the piezoelectric properties of P(VDF-TrFE)-based composites, which shows promising potential as a flexible sensor or energy harvester. In this work, we use the interaction between the magnetic nanofiller and magnetic field to modify the structure of CoFeO (CFO)@polydopamine (PDA)/P(VDF-TrFE) composite, in which CFO@PDA works as the nanofiller into the P(VDF-TrFE) matrix. It was found that the magnetic field orientation during polymer curing can significantly increase the content of the β-phase and of the composite. Regarding a typical composite film with 7 wt % CFO@PDA, the composite exhibits versatile sensing originated from the ball impact, hot-water droplet, bending, and pressing. In a noncontact magnetic field-driven experiment, the magnetic field oriented film produced the highest output voltages of 17.4 mV at 4 Hz and 12 mV at a drive amplitude of 19 Vpp, in contrast to the values of 7.1 mV and 7 mV for the film without magnetic field orientation, respectively. The LED without any charging capacitor can be instantaneously lighted through vertically pressing the oriented films. Thus, this work proposes a strategy of magnetic field orientation to improve the piezoelectric performance of the CFO@PDA/P(VDF-TrFE) multifunctional composite film.