(La0.6Ce0.4)65Al10Cu25 bulk metallic glasses (BMGs) were prepared by copper-mold casting. The crystallization behavior and thermal stability of (La0.6Ce0.4)65Al10Cu25 were investigated by X-ray diffraction and differential scanning caloricity (DSC). The isothermal kinetics was evaluated by the Johnson–Mehl–Avrami equation. The calculated Avrami exponents were in the range of 2.39 to 3.38. The average values of local Avrami exponents show that the value of n is about 3 at the initial stage; in the middle crystallization stage, the value of n changes from 2.5 to 3.5. In this stage, for 2.5