Understanding the polymerization process at the molecular level is essential for the rational design and synthesis of polymers with controllable structures and properties. Scanning tunneling microscopy (STM) is one of the most important techniques to investigate the structures and reactions on conductive solid surfaces, and it has successfully been used to reveal the polymerization process on the surface at the molecular level in recent years. In this Perspective, after a brief introduction of on-surface polymerization reactions and STM, we focus on the applications of STM in the study of the processes and mechanism of on-surface polymerization, from one-dimensional to two-dimensional polymerization reactions. We conclude by a discussion of the challenges and perspectives on this topic.