Eu-Ag co-doped borate glasses were prepared by the high temperature solid method in the present work. Absorption and emission spectra were employed to investigate the precipitation of Ag nanoparticles, which is influenced by the network form B2O3 and the co-doped Eu ions. It was found in the absorption spectra of Eu-Ag co-doped sample that a broad band centered at about 410 nm emerged and their intensity decreased with the increase in the B2O3 concentration. Meanwhile, under the excitation of 340 nm, a broad emission band was observed in the wavelength range of 350～600 nm, which belongs to the blue-green light of Ag aggregates. The intensity of the Ag aggregates presented an increasing tendency with the increase in the B2O3 contents. The weak characteristic emission of Ag aggregates and Eu3+ was observed respectively in their singly doped samples. It is concluded that both their emissions get significant enhancement when Eu ions and Ag ions are used for co-doping the sample. In addition, the increased absorption of Ag nanoparticles was detected with the increase in the Eu ions concentration. Herein, the mechanism behind Eu3+ contribution to the precipitation of Ag nanoparticles is discussed in detail. The luminescence properties of borate glasses can be controlled by the microstructure of the borate glasses. Therefore, the white emission can be realized by the adjustment of glass structure and Eu ions concentration, owing to the red light from Eu3+: 5D0→7FJ electronic transition and the blue-green light form the broad emission of Ag aggregates. The borate glasses are expected to be the candidates for the light-emission diode (LED) luminescent materials.