The feasibility of utilizing molybdenum tailing and diatomite as siliceous materials to prepare calcium silicate board was explored. The influences of molybdenum tailing/diatomite proportion on hydration characteristics, thermal conductivity, water absorption, flexural strength and moisture adsorption-desorption property of calcium silicate board were investigated in detail. The experimental results reveal that molybdenum tailing is environmentally friendly to prepare building materials. The main hydration products in calcium silicate board under autoclaved condition are C-S-H with low crystallinity and tobermorite. Molybdenum tailing is favorable to the formation of tobermorite. The flexural strength and bulk density of the calcium silicate board gradually increase when the content of molybdenum tailing increases. Netlike C-S-H is formed with the increase of diatomite content during autoclaved curing process, resulting in the enhancement of moisture adsorption-desorption performance and the reduction of thermal conductivity. The optimal content of molybdenum tailing is 20%, furthermore, the flexual strength and thermal conductivity of calcium silicate board at this content meet the Chinese standard JC/T564.1-2008.