Glass-ceramics were fabricated by heat-treatment of glass obtained by melting a coal bottom ash with Li2O addition. The main crystal grown in the glass-ceramics, containing 10 wt% Li2O, was β-spodumene solid solution, while in Li2O 20 wt% specimen was mullite, identified using XRD. The activation energy and Avrami constant for crystallization were calculated and showed that bulk crystallization behavior will be predominant, and this expectation agreed with the microstructural observations. The crystal phase grown in Li2O 10 wt% glass-ceramics had a dendrite-like shaped whereas the shape was flake-like in the 20 wt% case. The thermal expansion coefficient of the Li2O 10 wt% glass-ceramics was lower than that of the glass having the same composition, owing to the formation of a β-spodumene phase. For example, the thermal expansion coefficient of Li2O 10 wt% glass-ceramics was 20×10-7, which is enough for application in various heat-resistance fields. But above 20 wt% Li2O, the thermal coefficient expansion of glass-ceramics, on the contrary, was higher than that of the same composition glass, due to formation of mullite.