Zr-Al-Ni-Fe alloy series with different compositions were designed according to the criteria of constant electron concentration and atomic size. XRD results indicate that only the four alloys near the Zr-Al-Ni ternary system formed the bulk metallic glass. It is revealed by DSC and DTA curves that the best composition forming glass is Zr60.7Al15.5Ni15.5Fe8.3 with the thermodynamic characteristic parameters of Tg=710 K, Tx=770 K, ?Tx=60 K, Tg/Tm=0.607, and Tg/Tl=0.552, respectively.