In this work, we have prepared copper‐doped multicomponent tellurite glasses by solid state electric field‐assisted diffusion. The concentration profiles of the elements have been measured by the secondary ion mass spectrometry. The depth profile of copper can be well fitted only by a modified erfc‐like solution of the second Fick's law which assumes that both the Cu+ and Cu2+ ions are involved in the diffusion. The modeling shows that the Cu2+ ions are much more mobile than the Cu+ ones in the tellurite glasses and affected strongly by the applied electric field. Our results demonstrate the possibility of fabricating copper‐doped planar waveguides based on the tellurite glasses.