Substitutions of sulfate and aluminum ions in calcium silicate hydrate (tobermorite) were investigated at 175°C under saturated steam pressure. Structure and morphology of different tobermorite samples were investigated using XRD, FTIR and SEM. A sample of pure xonotlite was prepared to assist in FTIR band assignment of different tobermorites. Al 3+ decreases the degree of crystallinity at short curing time and increases crystallinity at longer curing times, with a sort of stabilization of small crystals. Al 3+ changes the morphology of tobermorite from platy-shape to lath-shape. Sulfate ion increases imperfection of tobermorite crystal structure and the morphology of tobermorite change magnificently to leafy shape. The FTIR spectra of all 1.1nm tobermorite samples are nearly similar. All tobermorite samples have a significant concentration of Q 3 Si sites, which indicates cross-linking of the chains. Sulfate substitution for silicate in tobermorite structure is associated with the appearance of the bands at 1610 and 631cm −1 which indicates the incorporation of CaO–H group in tobermorite structure. This indicated the charge compensation mechanism; SiO 4 4− is substituted by SO 4 2− and 2OH − .