The high-energy ball-milling (HEM) method was used to synthesize the compositions of BiNbO4, Bi5Nb3O15, and Bi3NbO7 in a Bi2O3-Nb2O5 binary system. Reagent Bi2O3 and Nb2O5 were chosen as the starting materials. The X-ray diffraction patterns of the three compositions milled for different times were studied. Only the cubic Bi3NbO7 phase, Nb2O5, and amorphous matters were observed in powders after being milled for 10 h. After heating at proper temperatures the amorphous matters disappeared and the proleptic phases of BiNbO4 and Bi5Nb3O15 could be obtained. The Scherrer formula was used to calculate the crystal size and the results of nanopowders are between 10 and 20 nm. The scanning electron microscopy photos of Bi3NbO7 powders showed drastic aggregation, and the particle size was about 100 nm. The dielectric properties of ceramics sintered from the nanopowders prepared by HEM at 100-1 MHz and the microwave region were measured. Bi3NbO7 ceramics showed a good microwave permittivity epsilon(r) of about 80 and a Q x f of about 300 at 5 GHz. The triclinic phase of BiNbO4 ceramics reached its best properties with epsilon(r)=24 and Q x f=14 000 GHz at about 8 GHz.