“…As an important fundamental phenomenon, the structural transformation of materials, which is associated with the change of their different structural parameters, including phase, composition, shape, facet, etc., under diverse external conditions, has drawn much research attention from both theoretical and experimental aspects. − In the transformation processes, the structure of starting materials plays a crucial role in determining the transformation pathway and modulating the resultant structures of intermediates and/or products. − Recently, increasing efforts have been devoted to the investigation of the structural transformation of starting materials with unconventional phases, which can not only unravel their thermodynamic stabilities in potential applications but also offer effective strategies for the synthesis of other unconventional-structured materials. Specifically, the identification of the structural evolution of unconventional-phase materials would lead to deep fundamental understanding of their structural stabilities and transformation mechanisms, providing important guidance to the stabilization strategy of unconventional phases and the exploration of their future applications. ,, Taking Au as an example, the transformation mechanisms from the unconventional 4H phase to the thermodynamically stable face-centered cubic (fcc) phase in Au nanostructures under diverse conditions, e.g., heating, high pressure, deformation, electron beam irradiation, etc., have been systematically investigated with the aid of various in situ techniques. Moreover, fine control over the transformation of unconventional-phase starting materials also represents an efficient approach toward the preparation of unconventional structures that normally cannot be obtained from conventional starting materials. ,− For instance, metastable intermediates and/or unconventional-structured products have been identified and obtained during the structural transformation of various amorphous starting materials, such as amorphous Pd–Ni–P alloy, amorphous Nb 2 O 5 , and amorphous Pd nanoparticles, demonstrating the feasibility of material synthesis via such transformation approaches.…”