The (Cu42Zr42Al8Ag8)100-xSix amorphous alloy rods, x =0 to 1, with 3 mm in diameter were prepared by Cu-mold drop casting method. The glass forming ability, thermal properties and microstructure evolution was studied by differential scanning calorimetry (DSC), and X-ray diffractometry (XRD). The XRD result reveals that these as-quenched (Cu42Zr42Al8Ag8)100-xSix alloy rods exhibit a broaden diffraction pattern of amorphous phase. The crystallization temperature and GFA (glass forming ability) of (Cu42Zr42Al8Ag8)100-xSix alloys increase with the silicon additions. The highest Trg (0.59) and γ value (0.405) occurred at the (Cu42Zr42Al8Ag8)99.75Si0.25 and (Cu42Zr42Al8Ag8)99.5Si0.5 alloy. In addition, both of the activation energy of crystallization and the incubation time of isothermal annealing for these (Cu42Zr42Al8Ag8)100-xSix alloys indicates that the (Cu42Zr42Al8Ag8)99.25Si0.75 alloy posses the best thermal stability among the (Cu42Zr42Al8Ag8)100-xSix alloy system.