The process of decay of photo-generated electrons in the conduction band of ZnO:Zn and ZnO powder materials after excitation with a ultra-short pulse laser has been investigated in this paper by microwave absorption method. The excitation and emission spectra of ZnO:Zn were measured at room temperature. It was measured that the lifetime o photoelectrons in the materials ZnOand ZnO:Zn are 64 ns and 336 ns respectively. It is believed that the increase of the lifetime in the material of ZnO:Zn is due to the prolong of relaxation time caused by the defect structure in the material.