Glass-ceramics have great potential as a dielectric material in energy storage. Grain refinement is an effective measure to improve the energy storage performance of dielectric materials. In this study, NaNbO 3 −Ba 0.27 Sr 0.75 Nb 2 O 6 (NN-BSN) complex glass-ceramic was prepared through the investigation and design of heat-treatment processes. The NN perovskite structure and BSN tungsten bronze structure are comparable, and heat treatment was employed to encapsulate the two phases, thereby achieving grain refinement. High-resolution transmission electron microscopy (HR-TEM) images were measured using Gatan Digital software, revealing a maximum lattice spacing of 0.067 nm in the selected area and a maximum interplanar spacing of 0.003 nm −1 in the SAED pattern. Furthermore, the influence of ZrO 2 and TiO 2 , with equal content, on the material structure and performance stability was studied. Raman analysis revealed that ZrO 2 exists as an intermediate network in the structure, resulting in good high-temperature stability of the samples. TiO 2 acted as a crystal nucleating agent, promoting grain growth and enhancing the polarization performance of the samples.