A high power 4.65 µm single wavelength laser by second harmonic generation (SHG) of TEA CO 2 laser pulses in silver gallium selenide (AgGaSe 2 ) and zinc germanium phosphide (ZnGeP 2 ) crystals is reported. Experimental results show that the average output power of SHG laser is not only restricted by the damage threshold of the nonlinear crystals, but also limited by the irradiated power of fundamental wave laser depending on the operating repetition rate. It is found that ZnGeP 2 can withstand higher 9.3 µm laser irra diation intensity than AgGaSe 2 . As a result, using a parallel array stacked by seven ZnGeP 2 crystals, an aver age power of 20.3 W 4.65 µm laser is obtained at 250 Hz. To the best of our knowledge, it is the highest output power for SHG of CO 2 laser by far.