Li/Mg separation and magnesium recovery as a high-value forsterite refractory material from the salt lake were investigated via the precipitation-calcination process. The combined Na₂SiO₃ and NaOH precipitants were applied for Li/Mg precipitation separation from salt lake brine and magnesium precipitates could be produced with various MgO/SiO₂ molar ratios. It is demonstrated that the magnesium precipitates were mainly composed of accumulative amorphous magnesium silicate and magnesium hydroxide, with more than 62% of mass residual at 1400 °C. The high- temperature sintering experiments showed that when the Mg/Na₂SiO₃/NaOH molar ratio was 1:0.6:0.8, the magnesium precipitates could be prepared into a high-quality refractory material under the conditions of 1350 °C and 210 min, with the refractoriness of higher than 1800 °C, compressive strength of 190.73 MPa, bulk density of 2.53 g/cm³, and apparent porosity of 5.94%. The prepared refractory materials mainly contained forsterite, with a minor enstatite phase.