The photoluminescence (PL) spectra of bulk α-In2Se3 crystals before and after 10 MeV electrons irradiation with the 1015 and 1017 cm−2 fluences were studied in the temperature range from 7 to 340 K. Three main types of radiative recombinations corresponding to band-to-tail (BT), deep defects, and band-to-band (BB) recombination were manifested in the non-irradiated α-In2Se3 crystals. Also recombinations that can be associated with exciton recombinations at temperatures below 45 K are observed. After electron irradiation, noticeable changes in the PL spectra are observed. We detected a slight increase in activation energy of the BT recombination. An increase in the concentration of deep defects is also noted. The significant decrease in PL intensity of the BB recombinations indicates the formation of non-radiative recombination centers after electron irradiation with the 1017 cm−2 fluence. Our study may be useful for understanding the effects of high-energy electrons irradiation on the performance of electronic and photovoltaic devices based on α-In2Se3.