Organosilicone composite antireflective (AR) coating was successfully prepared for Ti-sapphire crystals by sol-gel process from precursors of tetraethoxysilane [Si(OC2H5)4, TEOS] and methyltriethoxysilane [CH3Si(OC2H5)3, MTEOS]. This AR coating possessed prominent AR effect within the output waveband (750～850 nm) of Ti-sapphire laser with average transmission above 98.6%, and its surface homogeneity met the requirements of the laser wavefront. The laser induced damage threshold (LIDT) of 2.2 J/cm2 was obtained at 800 nm with the pulse duration of 300 ps for this AR coating on Ti-sapphire crystals, which made it suitable for the optics of ultrashort pulse pico- and femtosecond high power lasers. Further, investigations on the performance of coating solution showed that the viscosity and coating refractive index both increased along with MTEOS prepolymer content, and effect of bake temperature on the latter was very small.