Two-photon polymerization (TPP) is a cutting-edge micro/nanoscale three-dimensional (3D) printing technology based on the principle of two-photon absorption. TPP surpasses the diffraction limit in achieving feature sizes and excels in fabricating intricate 3D micro/nanostructures with exceptional resolution. The concept of 4D entails the fabrication of structures utilizing smart materials capable of undergoing shape, property, or functional changes in response to external stimuli over time. The integration of TPP and 4D printing introduces the possibility of producing responsive structures with micro/nanoscale accuracy, thereby enhancing the capabilities and potential applications of both technologies. This paper comprehensively reviews TPP-based 4D printing technology and its diverse applications. First, the working principles of TPP and its recent advancements are introduced. Second, the optional 4D printing materials suitable for fabrication with TPP are discussed. Finally, this review paper highlights several noteworthy applications of TPP-based 4D printing, including domains such as biomedical microrobots, bioinspired microactuators, autonomous mobile microrobots, transformable devices and robots, as well as anti-counterfeiting microdevices. In conclusion, this paper provides valuable insights into the current status and future prospects of TPP-based 4D printing technology, thereby serving as a guide for researchers and practitioners.