Chemical partitioning or segregation is commonly encountered in solid-state syntheses. It is driven by compositional, thermal and electric field gradients. These phenomena can be quite extreme in thin films and lead to notable effects on the electrical properties of ferroelectrics. The segregation in ferroelectric thin films will be illustrated and the mechanisms explained in terms of diffusion processes driven by a potential gradient of the oxygen. The hypothesis can also explain self polarisation and imprint in ferroelectric hysteresis.