In this paper, niobium-phosphate glasses doped with rare earths (Er and Sm) are investigated by Raman scattering. The goal of Raman characterization is twofold: (a) to perform a fine structural characterization of the synthesized glasses and (b) to measure the Raman gain coefficient of the samples and to compare it with fused silica. The results reveal the presence of NbO6 octahedra and Nb–O–P–Nb–O mixed chains. A broadening of bandwidth and a significant enhancement (∼24 times) in gain coefficient G with respect to conventional silica glasses are also demonstrated.