The effect of ball-to-powder weight ratio on the fabrication of Nb-base powder via ball milling was studied. The structural evolution and morphology of the powders were investigated using LPSA, XRD and SEM techniques. The results indicate that increasing the BPR leads to decreases in particle size and grain size of powders. For a given milling time of 18 h and rotational speed of 250 rpm, ball milling with BPR of 20:1 produces an ultrafine powder with a mean particle size of about 2 μm and a grain size of about 20 nm. A 30:1 of BPR increases the useless collision frequency during ball milling, leads to a serious fraying of milling balls.