With the growing need for sustainable energy technologies, advanced characterization methods become more and more critical for optimizing energy materials and understanding their operation mechanisms. In this review, we focus on the synchrotron-based X-ray imaging technologies, and the associated applications in gaining fundamental insights into the physical/chemical properties and reaction mechanisms of energy materials. We will discuss a few major X-ray imaging technologies, including X-ray projection imaging, transmission X-ray microscopy, scanning transmission X-ray microscopy, tender and soft X-ray imaging, and coherent diffraction imaging. Researchers can choose from various X-ray imaging techniques with different working principles based on research goals and sample specifications. With the X-ray imaging techniques, we can obtain the morphology, phase, lattice and strain information of energy materials in both 2D and 3D in an intuitive way. In addition, due to the high penetration of X-rays, operando/in-situ experiments can be designed to track the qualitative and quantitative changes of the samples during operation. We expect this review can broaden reader's view on X-ray imaging techniques and inspire new ideas and possibilities in energy materials research.