In the dynamic landscape of energy storage materials, the demand for efficient microstructural engineering has surged, driven by the imperative to seamlessly integrate renewable energy. Traditional material preparation methods encounter challenges such as poor controllability, high costs, and stringent operational conditions. The advent of microwave techniques heralds a transformative shift, offering rapid responses, high-temperature energy, and superior controllability. This review critically examines the nuanced applications of microwave technology in tailoring the microstructure of energy storage materials, emphasizing its pivotal role in the energy paradigm and addressing challenges posed by conventional methods. Notably, non-liquid-phase advanced microwave technology holds promise for introducing novel models and discoveries compared to traditional liquid-phase microwave methods. The ensuing discussion explores the profound impact of advanced microwave strategies on microstructural engineering, highlighting discernible advantages in optimizing performance for energy storage applications. Various applications of advanced microwave techniques in this domain are comprehensively discussed, providing a forward-looking perspective on their untapped potential to propel transformative strides in renewable energy research. This review offers insights into the promising future of leveraging microwaves for tailoring the microstructure of energy storage materials.