Glass-ceramics show a great application potential in sustainable development, environmental protection, high temperature, high voltage resistance, and so on. Given the breakdown strength has a great contribution to the energy storage density, alkali-free niobate-based glass-ceramics have emerged as a prominent energy storage material. In this study, the 13.64BaCO3-13.64SrCO3-32.72Nb2O5-40SiO2 alkali-free glass-ceramics were optimized in thickness and crystallization temperature. The thinning of thickness improves the breakdown strength. At the same time, the dielectric constant gets a maximum value by adjusting the crystallization temperature. Therefore, an ultra-high theoretical energy storage density of 27.47 J·cm−3 is obtained. In addition, the finite element software simulates the electric field distribution and electric potential evolution during the development of electric branches, which illustrates the role of glass phase in hindering the development of electric branches and partaking the high electric field. Finally, the effective energy storage density obtained by using P-E loops is 1.49 J·cm−3 under 850 kV/cm.