Using TiO2 and ZrO2 as compound nucleation agent, serials Li2O–Al2O3–SiO2 (LAS) glasses containing different content of P2O5 were prepared by conventional melt quenching technique and subsequent converting to glass–ceramics. The influence of P2O5 content on viscosity of LAS glasses was investigated in the temperature range from the softening point to melting temperature. DSC was undertaken to analyze the change of characteristic temperature Tg, Tc and Tp. Thermal expansion coefficient (TEC) of matrix glass and glass-ceramic containing different P2O5 were measured. The results show introducing P2O5 effectively decreased the melting temperature and viscosity of LAS glasses. TECs of the matrix glass and glass-ceramic range from 4.1×10-6 °C -1 to 5.3×10-6 °C -1 and from -0.2×10-6 °C -1 to 1.2×10-6 °C -1, respectively. XRD analysis indicates that β-spodumene is the main crystalline phase in the P2O5 doped LAS glass-ceramics, resulting in the low thermal expansion coefficient of the glass-ceramics.