Both silica and boron-silica glass materials doped with terbium organic complex were prepared by in situ sol-gel method respectively. XRD and SEM measurements were performed to verify the non-crystalline structure of the glass. The influence of the glass contents on the structure of the glass and the energy level of the doped Tb (III) ions was analyzed by the emission spectra and IR spectra. The effect of B2O3 on the photoluminescence properties of rare earth organic complex in silica-based glass was investigated. The IR spectra indicate that the in situ synthesized rare earth complex molecule was confined to the micropores of the host and the vibration of the ligands was frozen. When B2O3 was added into the silica host gel, B2O3 had little influence on the non-crystalline structure of the glass, and BO3 triangle, which had a layer structure different from the silica framework, could form. So the silica network became more inhomogenous, and the luminescence of terbium complexes was quenched with the increase of the B2O3 amount.