Recently, large-scale accidents caused by minor damage from fatigue failure and impact on structures have been frequently reported. Therefore, a real-time damage monitoring system of structures is considered to be one of the most important technologies to ensure safety in various types of research. The piezoelectric sensor, which has an advantage of converting deformation of a structure into an electrical signal without using an additional power source, has been reported as one of the most suitable methods for real-time monitoring systems. This review aims to describe the structural monitoring system utilizing piezoelectric paint sensors. First, we present the concept of a piezoelectric paint sensor with the advantages of flexibility and piezoelectric performance. Then, factors affecting the performance of the piezoelectric paint sensor are introduced. Finally, an overview of piezoelectric paint sensors for structural monitoring, such as vibration detection and impact monitoring, are provided. The state-of-the-art of the application of the piezoelectric sensor is also introduced, providing feasibility in industrial fields.