The study of 3D structure design is essential because well-defined 3D structures are a prerequisite to the exploration of chemical space in order to understand, for example, conformational space or to investigate complex chemical reaction mechanisms. Extensive research effort has been expended toward understanding the representation of chemical structures, along with the development of automatic 3D structure generation. Whereas most methods for de novo design are developed for drug-like organic molecules, successful strategies, to a lesser extent, have been explored in organometallic and transition metal chemistry. The potential applications of TMCs, ranging from catalysis and materials science to medicine and environmental technology, underscore the importance for this area of research. As a broad class, organometallic molecules are much more complex and structurally diverse than organic molecules, which poses new challenges to the discovery of novel structures in transition metal chemistry, requiring an in-depth understanding of both theoretical and experimental principles. Herein, we provide a concise overview of various methods for the discovery of inorganic materials, with a focus on TMCs.