Cathodoluminescence (CL) and secondary electron emission (SEE) in the scanning electron microscope have been used to study the effects of mechanical polishing and electron irradiation on YBa2Cu3O7‐x ceramics. CL spectra from the mechanically polished superconductors show an enhanced 2.4 eV luminescence band, which is related to oxygen content redistribution or depletion. Electron irradiation induces strong morphological and compositional changes which are proposed to be connected with melting‐resolidification processes and surface phase segregation. SEE yield measurements allow to detect an oxygen depleted area with stoichiometric cationic composition surrounding the irradiated region. CL spectra recorded from this oxygen‐deficient area also show an enhanced 2.3 to 2.4 eV emission band in comparison with the spectra recorded from the non‐irradiated material. Strongly luminescent non‐superconducting phases appear in the irradiated regions, showing intense 3.1 and 0·78 to 0·81 eV emission bands.