Synthesis of diphenyl carbonate (DPC) from dimethyl carbonate (DMC) with phenol is the most prominent application of transesterification of dialkyl carbonates (DACs); this is a significant step for the nonphosgene manufacturing of polycarbonate, which is considered to be one of the best examples of green and sustainable transformations available on such a large scale. In the last decades, extensive efforts have been focusing on atom efficiency, increased safety, waste avoidance, and other process improvements for the transesterification synthesis of DPC. However, low product selectivity, separation, and catalyst deactivation remain bottlenecks of the process, despite recent significant progress. Therefore, the present interest focuses on rational design of highly efficient and stable catalysts. However, there is still a lack of a comprehensive summary on catalyst design and mechanism involved. Therefore, in this work, transesterification of DMC with phenol has been critically revised as a model case, to illustrate the structure-performance correlation and reaction pathways for transesterification with phenols. In this perspective, recent advances on experimental and investigations on rational design of heterogeneous catalysts, for facile liquid-phase reaction of DMC with phenol, have been systematically discussed, in terms of catalyst synthesis, surface characterization, and structure-function relationship. More importantly, plausible mechanisms for transesterification of DMC with phenol will be systematically discussed with the aim to provide insights into fundamental understanding on transesterification chemistry and improvement of activity, selectivity, and stability of these catalytic materials.