Sintering glass-ceramics, a new type material for architectural decoration, belong to CaO-Al2O3-SiO2 system (CAS) without nucleation agent. Combined by Differential thermal analysis (DTA), X-ray diffraction (XRD), Scanning electron microscopy (SEM) and Transmission electron microscope (TEM), phase evolutionary process of CaO-Al2O3-SiO2 system glass and glass-ceramic was investigated. According the relation between heat treatment schedule and microstructure, the glass system has a very wide temperature range of crystallization. The crystalline phase is β-CaSiO3 (β-wollastonite) and there is no other crystalline phases precipitated in these glass-ceramics. The influences of various heat treatment systems on the structure and properties of the glass-ceramics were investigated simultaneously. The optimal heat treatment schedule, microstructure and bending strength of the CAS glass ceramic were gained.