This paper reports on the photoluminescence spectra of ZnSe single crystal with trace chlorine excited by the femtosecond laser pulse. Three emission bands, including second-harmonic-generation, two-photon-excited peak and a broad band at 500-700nm, were detected. The thermal strain induced by femtosecond pulse strongly influences the photoluminescence of ZnSe crystal. The corresponding strain e in ZnSe crystal is estimated to be about 8.8 × 10-3 at room temperature. The zinc-vacancy, as the main point defect induced by femtosecond pulse, is successfully used to interpret the broad emission at 500-700nm. The research shows that self-activated luminescence possesses the recombination mechanism of donor-vacancy pair, and it is also influenced by a few selenium defects and the temperature.The rapid decrease in photoluminescence intensity of two-photon-excited fluorescence and second-harmonic generation emission at lower temperature is attributed to the fact that more point defects result in the thermal activation of the two-photo-absorption energy converting to the stronger recombination emission of chlorine-zinc vacancy in 500-700nm. The experimental results indicate that the femtosecond exciting photoluminescence shows a completely different emission mechanism to that of He-Cd exciting luminescence in ZnSe single crystal. The femtosecond laser exhibits a higher sensitive to the impurity in crystal materials, which can be recommended as an efficient way to estimate the trace impurity in high quality crystals.