To prepare magnesium hydroxide is one of the effective methods to the comprehensive utilization of asbestos tailings. Nano-scale magnesium hydroxide was prepared and mechanisms of in-situ surface modification were characterized in the paper. Process conditions of preparation of magnesium hydroxide from purified hydrochloric acid leachate of asbestos tailings were optimized and in-situ surface modification of the product was carried out. Results showed that optimum process conditions for preparing nano-scale magnesium hydroxide were as follows: initial concentration of Mg²⁺ in the leachate was 22.75g/L, precipitant was NaOH solution (mass concentration 20%), reaction temperature was 50°C, and reaction time was 5min. The diameter and thickness of the plate nano-scale magnesium hydroxide powder prepared under optimal conditions were about 100 nm and 10 nm, respectively. However, particle agglomeration was obvious, the particle size increased to micron-grade. Dispersity of the magnesium hydroxide powder could be elevated by in-situ modification by silane FR-693, titanate YB-502 and polyethylene glycol and optimum dosages were 1.5%, 1.5% and 0.75% of the mass of magnesium hydroxide, respectively. All of the modifiers adsorbed chemically on surfaces of magnesium hydroxide particles, among which Si-O-Mg bonds formed among silane FR-693 and the particle surfaces and Ti-O-Mg among titanate YB-502 and the surfaces.