Unlike α- and γ-mode operation, electrons accelerated by strong drift and ambipolar electric fields in the plasma bulk and at the sheath edges are found to dominate the ionization in strongly electronegative discharges. These fields are caused by a low bulk conductivity and local maxima of the electron density at the sheath edges, respectively. This drift-ambipolar mode is investigated by kinetic particle simulations, experimental phase-resolved optical emission spectroscopy, and an analytical model in CF(4). Mode transitions induced by voltage and pressure variations are studied.