This paper aimed at improving high-frequency magnetic properties and decreasing material cost of “Finemet”alloy without sacrificing saturation magnetization (Ms) and coercivity (Hc) by minor V and Mo substitution of Nb. Both V and Mo enhanced glass forming ability (GFA) and promoted the precipitation of primary α-Fe particles. Meanwhile, V addition hindered the precipitation of the secondary phase and consequently extended annealing temperature range. After annealing, the Fe73.5Si15.5B9Cu1Nb2V1 and Fe73.5Si15.5B9Cu1Nb2.5Mo0.5 have high Ms of 129.0 and 127.6 emu/g, low Hc of 2.7 and 5.3 A/m, and high μe of 3.6 × 104 and 3.4 × 104 at 200 kHz/0.3V respectively. The order of the effect of Nb, Mo and V on decreasing grain size and coercivity (Hc) is Nb>V>Mo. Besides, the increasing electrical resistivity via adding 1.0 at.% V and 0.5 at.% Mo contributed to a higher and more stable effective permeability (μe) in a wide high frequency range. These advantages for soft magnetic materials are promising for high-frequency applications.