Element Sn is substituted for metalloid elements Si and B in the Ti50Ni22Cu18Al4Si4B2 alloy to form the Ti50Ni22Cu18Al4Snx(Si0.67B0.33)6-x (x=0, 3, 6) series alloys for high-energy ball milling. For comparison, the amorphous alloy ribbon with a composition of x=6 was prepared using melt-spinning method as well. Structural features of the samples were characterized using x-ray diffraction, transmission electron microscopy and differential scanning calorimetry. In the ball-milled alloys, the fraction of residual α-Ti crystallites in the final products was reduced with increasing the Sn content. For the Ti50Ni22Cu18Al4Sn6 alloy, without any metalloid element, the complete amorphization is achievable. Such a ball-milled glassy alloy shows the thermal properties comparable with those of the melt-spun glassy ribbon with the same composition, and exhibits the largest supercooled liquid region about 66 K.