Magnetoelectric multiferroic materials, particularly with the perovskite structure, are receiving a lot of attention because of their inherent coupling between electrical polarization and magnetic ordering. However, very few types of direct coupling between polarization and magnetization are known, and it is unclear whether they can be useful to the design of spintronic devices exploiting the control of magnetization by electric fields. For instance, the typical biquadratic coupling only allows changing the magnitude of the magnetization by an electric field, but it does not permit an electric-field-induced switching of the magnetization. Similarly, the so-called Lifshitz invariants allow an electric-field control of complicated magnetic orderings, but not of the magnetization. Here, we report on original direct couplings between polarization and magnetization in epitaxial perovskite films, via the use of first-principles methods and the development of an original Landau-type phenomenological theory. Our results feature pentalinear interactions involving the ferromagnetic and antiferromagnetic vectors as well as the polar distortions and oxygen octahedral tilting, and permit a number of striking effects. Examples include a continuous electric-field control of the magnetization magnitude and sign, and the discrete switching of the magnetization magnitude. Thus, the high-order, pentalinear couplings demonstrated in this work may open paths towards specific magnetoelectric effects, as well as spintronic and magnonic devices.