By the ultra-cavity single-pass configuration, stimulated Raman scattering(SRS) of LiIO3 crystal was realized. When the pump source was a 532 nm picosecond laser, three Stokes lines (556.07, 582.30, 611.76 nm) and one anti-Stokes line (509.57 nm) were observed, and the frequency shifting was calculated to be 820 cm-1. The SRS thresholds and Raman gain coefficients for different scattering lines were measured, and the total conversion efficiency reached 56%. Picosecond, external resonator Raman laser was realized based on LiIO3 crystal, the total conversion efficiency for dual-wavelength output was 27%, and the largest output energy was 1.4 mJ.