Developing smart transportation and advocating green transportation are the main directions of future transportation development. In recent years, with the rapid development of intelligent structures and intelligent materials, a variety of energy harvesting technologies in road environment have gradually become a research hotspot. However, due to the low energy conversion efficiency and high cost, the application of some energy harvesting technologies is limited. Among them, vibration energy capture technology based on piezoelectric effect has been widely concerned by scholars because it does not need external power supply and can supply power for low-power wireless sensors. Therefore, this paper summarizes the current state of road energy harvesting technology, with emphasis on piezoelectric systems. It includes the mechanism of piezoelectric effect, the structure of the collector, and its road application. Based on extensive review research, this paper provides a comprehensive insight into road energy harvesting technologies. Specifically, the paper discusses the social and environmental benefits and challenges of road energy harvesting technologies. Finally, research on the durability, safety, and life cycle cost of road piezoelectric energy capture technology is still scarce. It is recommended to carry out such research in order to promote the positive contribution of piezoelectric energy exchange technology in the construction of intelligent transportation.