The purpose of this study was to find out glass compositions permitting to obtain glass-ceramics of the Cr4+:Ca2GeO4 nanophase with a proper condition of syntheses and satisfying the requirements for transparent glass-ceramic. Three series of glass compositions were investigated, containing CaO, GeO2 and the glass formers: CaO-GeO2-B2O3, CaO-GeO2-Na2B4O7 and CaO-GeO2-LiBO2. The comparison between the three systems clearly shows that CaO-GeO2-LiBO2 offers significantly better conditions for obtaining glass ceramics containing Ca2GeO4 nanophase, as regards the temperature of melting and homogenization of the glasses (1100–1150°C) and the possibility of obtaining Ca2GeO4, as a phase into the glass. It was established that because of the big difference between the speed of nuclei and the speed of particle growth, particles at about 50nm at high degree of crystallization can be received. Transmission and photoluminescence spectra are measured and show that the active ion is Cr4+. A broad–band of emission in the range of 1000–1600nm was established.