In this study, (Cu36Zr48Al8Ag8)100-xSix (x = 0–1) amorphous alloy rod with (2~4) mm diameter were prepared by arc melting. The thermal properties and microstructure development during the annealing of amorphous alloys have been investigated by the combination of differential scanning calorimetry (DSC),, X-ray diffractometry (XRD) and Vickers indentation. The XRD result reveals that all these as-quenched, (Cu36Zr48Al8Ag8)100-xSix alloys exhibit the broad diffraction patterns of amorphous phase. A clear Tg (glass transition temperature) and supercooled region (about 102 K) were revealed for all of those amorphous alloy rods. The crystallization temperature (Tx), (ΔTx) , and micro-hardness of (Cu36Zr48Al8Ag8)100-xSix amorphous alloys is increased as the Si content.