A systematic series of silicon (Si) wafer with microstructured anti-reflection film is prepared by femtosecond laser pulse. The dependence of the morphology and optical properties of the microstructured Si on the experimental parameters is thoroughly investigated. With the laser pulse duration of 40 fs, central wavelength of 800 nm, repetition rate of 250 kHz, laser pulse power of 300 mW, 250 \mu m/s scanning speed, and 2 \mu m of displacement between the parallel scans in the air, the quasiordered arrays of grain microstructures on the Si wafer up to 800-nm tall and 800-nm diameter at the bottom offered near-unity transmission in the mid-infrared wavelength. An anti-reflection film of approximately 3 \times 3 (mm) is developed on the (211) Si substrate with the optimized parameters, Moreover, up to 30% improvement of the response performance is demonstrated.