The LAS glass containing P2O5 has been prepared by conventional molten quenching method. The influence of heat treatment conditions on crystallization behavior, including phase transformation and microstructure, and thermal expansion coefficient (TEC) of Li2O–Al2O3–SiO2 (LAS) glass-ceramics were investigated. DSC, XRD, SEM and TEC were used to detect the microstructure and properties of glass-ceramics under the different heat-treatment conditions. The results show the virgilite crystalline separated firstly from the matrix glass when heat treatment temperature was 850 °C. As the heat treatment temperature increased from 850 °C to 1050 °C, virgilite and β-spodumene were identified as main crystal phases. The TEC of glass-ceramics ranges from 0.5×10-6 °C-1 to 2.8×10-6 °C-1, which is much lower than that of matrix glass.