Optical absorption and emission spectra of Eu3+ in Ba(PO3)2, Zn(PO3)2, and Pb(PO3)2 glasses are reported. Judd-Ofelt intensity parameters for f-f transitions were derived from the integrated absorption spectra and used to calculate the spontaneous emission probabilities from the 5D0 state. Fluorescence-line-narrowed emission excited by the 5D0 7F0 transition was used to study local structure around the Eu3+ ion. A phenomenological crystal-field analysis was conducted using C2v symmetry, and it was found that the sites occupied by Eu3+ in the glasses are adequately described by Brecher and Risebergs model. The influence of the network modifier ions (Ba, Zn, and Pb) on the major crystal-field parameter ratio (B22/B20 and B44/B40) is discussed. Furthermore, it was shown that the network modifier ions affect the properties of the Eu-O bond, and, consequently, the crystal-field strength. © 1990 The American Physical Society.