In this study, we studied the nature of products obtained from the solution method in the borate oxide of the formula 47B2O3·(26-x/2)CaO·(24-x/2)Na2O·3P2O5·xZnO (0≤x ≤ 8 mol%). Precipitation due to the different reactivities between the solution of boric acid and the precursors was separated through a filtration process. Filtered powders were heat-treated at 400, 500 and 600 °C for 2h. Evaporated powders with the same compositions have been obtained by evaporating solutions at 80 °C and then powders treated at 600 °C for 2h. The structure evolution of as-prepared, filtered, and evaporated, powders and sintered powders at different temperatures was followed by thermogravimetric analysis TGA, X-ray diffraction and Infrared spectroscopy. As a result of precursor reactions in solution, the filtered powders mainly consist of crystalline B5H5Na2O11, Ca(CO3), Na2HPO3(H2O)5 and Zn(B3O3(OH)5)H2O phases. The crystalline Zn(H2O)B2O4.0.12H2O phase appears in the composition containing 8 mol% of ZnO. The amorphous phase formation is related to the preparation conditions. The construction of evaporated powders is an amorphous borate phase superimposed with those crystalline phases observed in filtered powders. The residual components of unreacted precursors (H2O, CO2) were eliminated by sintering up to 400 °C, at which condensation reaction was clearly observed. Crystalline B3CaHO6 and pentaborate B5H5Na2O11 phases are a result of heat-treatment at 400 and 500 °C. While heat treatment of filtered powders at 600 °C, crystalline phases mainly transform to the borate phase with non-bridging oxygen atoms including Na3BO3, B2CaO4, and orthophosphate CaNaO4P phase. The most significant results are from the sample containing 8 mol% of ZnO. There is a fraction of ZnO that forms a tetrahedral ZnO4 phase and remains stable overheat treatment of the filtered powders. In the evaporated powders heat-treated at 600 °C, the amorphous phase acts as a host matrix for further of ZnO, and ZnO has a modifier role.