Density-functional calculations are employed to investigate the effect of ferroelectric polarization of BaTiO(3) on the magnetocrystalline anisotropy of the Fe /BaTiO(3)(001) interface. It is found that the interface magnetocrystalline anisotropy energy changes from 1.33 to 1.02 erg cm (-2) when the ferroelectric polarization is reversed. This strong magnetoelectric coupling is explained in terms of the changing population of the Fe 3d orbitals at the Fe/BaTiO(3) interface driven by polarization reversal. Our results indicate that the electronically assisted magnetoelectric effects at the ferromagnetic/ferroelectric interfaces may be a viable alternative to the strain mediated coupling in related heterostructures and the electric field-induced effects on the interface magnetic anisotropy in ferromagnet/dielectric structures.