In fabricating plasma display panels, the photolithographic process is used to form patterns of barrier ribs with high accuracy and high aspect ratio. It is important in the photolithographic process to control the refractive index of the photosensitive paste. The composition of this paste for photolithography is based on the B2O3-SiO2-Al2O3 glass system, including additives of alkali oxides and rare earth oxides. In this work, we investigated the density, structure and refractive index of glasses based on the B2O3-SiO2-Al2O3 system with the addition of Li2O, K2O, Na2O, CaO, SrO, and MgO. The refractive index of the glasses containing K2O, Na2O and CaO was similar to that of the [BO3] fraction while that of the SrO, MgO and Li2O containing glasses were not correlated with the coordination fraction. The coordination number of the boron atoms was measured by MAS NMR. The refractive index increased with a decrease of molar volume due to the increase in the number of non-bridging oxygen atoms and the polarizability. The lowest refractive index (1.485) in this study was that of the B2O3-SiO2-Al2O3-K2O glass system due to the larger ionic radius of K+. Based on our results, it has been determined that the refractive index of the B2O3-SiO2-Al2O3 system should be controlled by the addition of alkali oxides and alkali earth oxides for proper formation of the photosensitive paste.