Flexible polymer-based magnetoelectric (ME) materials have broad application prospects and are considered as a new research field. In this article, FeCoSiB thin films were deposited on poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) substrate by DC magnetron sputtering. The structure of PVDF-TrFE/FeCoSiB heterostructure thin films was similar to 2-2. Under a bias magnetic field of 70 Oe, the composites have a dramatically increased ME voltage coefficient as high as 111 V/cm⋅Oe at a frequency of about 85 kHz. The piezoelectric coefficient of PVDF-TrFE thin films is 34.87 pC/N. The surface morphology of PVDF-TrFE thin films were studied by FESEM, and the results of XRD and FTIR showed that the β-phase of PVDF-TrFE thin films was dominant. Meanwhile, the effects of different heating conditions on the crystallization and piezoelectric properties of PVDF-TrFE films were also studied. The flexible ME heterojunction composite has a significant ME voltage coefficient and excellent piezoelectric properties at room temperature, which allows it to be a candidate material for developing flexible magnetoelectric devices.