Polymer-derived ceramics technology has become one of the main preparation technologies for ceramics and ceramic composite materials due to the advantages of flexible designability of polymer molecules, easy molding and low preparation temperature. Pyrolysis is a key step for the preceramic polymer to transform from organic to inorganic, and plays a decisive role on the composition, structure and properties of the target ceramics. By adding transition metals to the preceramic polymers for catalytical pyrolysis, the pyrolysis behavior was tailored to regulate and expand the structure and performance of the pyrolyzates. The catalytical pyrolysis effects of different transition metals on preceramic polymers were reviewed, the research status was summarized, the catalytical mechanism was discussed, and the development suggestions for the subsequent research and application were proposed.