The charge-mediated effect of electric field on the perpendicular magnetic anisotropy (PMA) of Fe/MgO interfaces is investigated using first-principles calculations. We present an approach by discussing this effect in relation to the intrinsic dipole field existing at the Fe/MgO interface. A firm correlation between the PMA and the interfacial dipole is established and further verified in the absence of an applied electric field. The on-site projected PMA analysis not only elucidates that the effect of electric field on the PMA extends beyond the interfacial Fe layer, but also shows that the second Fe layer carries the largest contribution to the effect. This observation is interpreted in relation to the orbital hybridization changes induced by applying an electric field.