Theoretical and experimental determinations show that the intrinsic luminescence of BGO materials is strongly influenced by GeO4- tetrahedra around Bi3+ ions. Besides Bi3+ transitions, the excitonic spectra mask the BGO bandgap. Theoretical computations give the bandgap at 5.19 eV compared with the experimental one at 5.17 eV in BGO crystals and a significant decrease at 3.26 eV in the amorphous materials. This is due to the high disordering of the GeO4- tetrahedral which also reduces the refractive index of the amorphous materials. Formation of excitonic states and their overlap with the Bi3+ transitions suggests that the energy absorption takes place via the p-electrons of the O-2(-) ions and is then transferred to the Bi3+ p-electrons (excited states) close to the conduction band. Light emission appears after de-excitation to the ground state. (C) 2010 Elsevier Ltd. All rights reserved.