The pre-reaction temperature effects on the crystallization and micro-structure of xonotlite for C-S-H gels with Ca/Si ratio = 1 using a steam assisted crystallization process was investigated. The pre-reaction temperature affected the crystallinity, pore structure and silicate chain structure of C-S-H gels, thereby influencing the xonotlite micro-structure and formation kinetics. A higher Q 2 /Q 1 Si peak intensity ratio were observed in C-S-H gels prereacted at 80°C, indicating that a higher pre-reaction temperature can promote condensation reactions between the Si-OH units, and hence transforming of silicate chain structure from a single chain structure to a double chain structure. The XRD background intensities around 2H = 20°-35°resulting from the occurrence of amorphous C-S-H phase decreased as the pre-reaction temperature increased, suggesting that the pre-reaction temperature can increase the degree of structural order and crystallinity. More xonotlite were formed for C-S-H gels pre-reacted at 40°C and 60°C after reacting at 180°C for 32 h and 190°C for 16 h compared to the sample pre-reacted at 80°C, due to the decrease of the solubility resulting from the increase of the average silicate chain length and the decrease of Ca/Si ratio after pre-reaction at 80°C.