Diffusion properties of Sc3+ in LiNbO3 crystal were studied, together with other two related issues: Sc3+-doping effect on LiNbO3 refractive index and Li2O out-diffusion arising from Sc3+ in-diffusion. To reach the goal, some Sc3+-doped LiNbO3 crystal plates were prepared by in-diffusion of Sc2O3 film coated onto Z-cut congruent substrates in air at different temperatures ranging from 1030°C to 1130°C. After diffusion, the refractive indices at the doped and undoped parts of surface were measured by prism coupling technique and the surface composition was evaluated from the measured index. The results show that the Sc3+ doping has little contribution to the substrate index and the Li2O out-diffusion is not measurable. The Sc3+ profile was analyzed by secondary ion mass spectrometry. Some characteristic parameters such as temperature-dependent diffusivity, diffusion constant, activation energy, and surface concentration are obtained. The Sc3+/Ti4+ co-diffusion characteristics were also studied. Comparison shows that in the single-diffusion case, the Sc3+ diffusivity is considerably smaller than the Ti4+ diffusivity. In the Sc3+/Ti4+ co-diffusion case, the Ti4+ co-diffusion results in substantial increase in Sc3+ diffusivity while the Ti4+ diffusivity changing little. The diffusion characteristics are qualitatively explained. The Ti4+-assisted Sc3+ diffusion would be utilizable in shortening the fabrication period of an optical-damage-resistant Ti-diffused LiNbO3 waveguide doped with Sc3+, and some considerations for the fabrication are given.