The mechanism of field-effect doping in the 123 high critical temperature superconductors (HTS) has been investigated by x-ray absorption spectroscopy in the presence of an electric field. We demonstrate that holes are created at the CuO chains of the charge reservoir and that field-effect doping of the CuO(2) planes occurs by charge transfer, from the chains to the planes, of a fraction of the overall induced holes. The electronic properties of the charge reservoir and of the dielectric-HTS interface determine the electric field doping of the CuO(2) planes.