A first principles continuum analytical model for cationic segregation to the grain boundaries in complex ceramic oxides is presented. The model permits one to determine the electric charge density and the segregation-induced electric potential profiles through the grain and can be extrapolated to the range of nanostructured grain sizes. The theoretical predictions are compared with existing data for yttria-stabilized tetragonal zirconia polycrystals. The implications for physical properties (mainly high temperature plasticity and hardening behaviour) are then discussed.