The photoluminescence spectra of CuI crystals using synchrotron radiation as an excitation light source were obtained at 60K. The emission peaks at 405, 415, 420 and 443nm were observed respectively. The possible origins of these peaks were discussed by the temperature dependence of CuI luminescence. Meanwhile, the photoluminescence spectra of CuI powder with different excitation intensity were measured and the ultrafast component luminescence in CuI crystals was warranted to be attributed to the donor acceptor pair recombination. Furthermore, the excitation process was understood by the photoluminescence excitation spectra of CuI crystals and powder.

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