Abstract: Bulk metallic glass (BMG) formation was explored in the Fe-B-Si-Nb alloy system though combined use of the atomic cluster line approach and the minor alloying strategy. The basic ternary compositions in the Fe-B-Si system were determined by the intersection points of two cluster lines, namely, Fe-B cluster to Si and Fe-Si cluster to B. 3at%–4at% Nb was added to the quaternary Fe-B-Si-Nb alloy. The casting experiments revealed that good glass-forming ability (GFA) occurred at the (Fe_73.4Si_8.2B_18.4)₉₆Nb₄ composition, and 3-mm diameter BMG samples were made. The glass transition temperature (T_g), crystallization temperature (T_x), and supercooled liquid region (ΔT_x=T_x-T_g) of this BMG were measured to be 866, 889, and 23 K, respectively. The BMG shows a high Vickers hardness of about Hv 1164, a Young’s modulus of 180 GPa, and a good corrosion resistance in the solutions of 1 mol/L HCl and 3wt% NaCl.