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Fe2+:ZnSe thin films are prepared on sapphire substrate at room temperature by electron beam evaporation and then annealed in vacuum (about 1 × 10-4 Pa) at different temperatures. The infl uences of thermal annealing on the structural andoptical properties of these films such as grain size and optical transmittance are investigated. The x-ray diffraction pattesshow that the Fe2+:ZnSe thin film is preferred to be oriented along the (111) plane at different annealing temperatures. After the film is annealed, the full-width-at-half-maximum ( FWHM ) of the x-ray diffraction peak profile (111) of the film decreases and its crystal quality is improved. Scanning electron microscope images show that the films are more denseafter being annealed. Finally, the sample is used as a saturable absorber in ZBLAN fiber laser. The annealed Fe2+:ZnSe thin films can be used to realize stable Q-switching modulation on ZBLAN fiber laser. The results demonstrate that theFe2+:ZnSe thin film is a promising material for generating the high-power pulses of mid-infrared Q-switched fiber lasers.