Low‐temperature photoluminescence spectra are presented for Si crystals which have been irradiated with high‐energy electrons. Studies of isochronal annealing, stress effects, and the temperature dependences of the luminescence are used to discuss the nature of the luminescent transitions and the properties of defects. Two dominant bands present after room‐temperature anneal of irradiated material are discussed, and correlations of the properties of these bands are made with known Si defects. A band between 0.8 and 1.0 eV has properties which are related to those of the divacancy, and a band between 0.6 and 0.8 eV has properties related to those of the Si‐G15 (K) center. Additional peaks appear in the luminescence after high‐temperature anneal; the influence of impurities and the effects of annealing on these lines are discussed.