Magnetoelectric effect at Fe3Si/BaTiO3 (001) interfaces is investigated by using the first-principles calculations. Interfacial separation works reveal that the FeSi/TiO2 and modified FeFe/TiO2 and SiSi/TiO2 interfaces are more stable than the Fe/TiO2 interface. While for the modified SiSi/TiO2 interface, the paraelectric phase is recovered in BaTiO3 slab due to its symmetrical structure in the central TiO2 layer. Compared with the original Fe/TiO2 and FeSi/TiO2 interfaces, more net change magnetizations are achieved at modified FeFe/TiO2 interface. The predicted magnetoelectric effect opens a direction to control magnetic properties of thin-film layered structure by electric fields. (C) 2013 Elsevier B.V. All rights reserved.