High energy ball milling method was employed to prepare the amorphous Ti50Ni22Cu25Sn3 alloy powders, and the effects of the ball milling parameters on the formation of the amorphous alloy were investigated. Results indicate that the rotation speed and ball diameter have a significant influence on the formation efficiency of the amorphous phase. High rotation speed and proper ball diameter can shorten the time to form the amorphous phase. At the rotation speed of 400 r/min and the mass ratio 20:1 of the ball to the powders, the completely amorphous Ti50Ni22Cu25Sn3 alloy powders can be obtained after ball milling for 30 h