Ferroelectric/piezoelectric perovskites are an important class of functional material and have broad application prospects in commercial, industrial, military and other areas because of their high dielectric constants, high piezoelectric coefficients, and high electromechanical coupling coefficients. Their structures, applications, and physical mechanisms have been intensively studied in condensed matter physics and material science. The piezoelectric properties of ferroelectric materials mainly originate from the intrinsic field-induced lattice distortion and extrinsic domain inversion and domain wall motion. Therefore, the understanding of and the distinguishing between these mechanisms are important for ascertaining the origin of the high-piezoelectric properties and developing new functional materials. In this article, we review the research progress of technical means and methodology of analyzing the changes of crystal lattices and magnetic domains of materials under the action of an externally applied electric field through the high-energy synchrotron X-ray diffraction experiments. The techniques and analysis methods involved in the review cover the time-resolved X-ray diffraction, single/double-peak analysis, full-pattern refinement, center-of-mass calculation, and field-induced phase transformation analysis, which are used to study the intrinsic and extrinsic contributions to sample’s macroscopic properties. It is expected to provide the research methods, which fulfill the individual experimental requirements, and the technical support for the mechanism analysis of various piezoelectric materials through the introduction and review of various methods.