The fixation of CO2 into high-value chemicals has emerged as a critical research priority, attracting considerable interest from both academia and industry. The synthesis of cyclic carbonates via the cycloaddition of CO2 with epoxides, a process exhibiting 100% atom economy, exemplifies a highly desirable reaction aligned with the principles of “green chemistry” and “atomic economy”. Cyclic carbonates find widespread applications in lithium-ion batteries, pharmaceutical manufacturing, and various fine chemical industries. This review provides a comprehensive overview of recent advances, challenges, and perspectives in the field of CO2 cycloaddition reactions. Initially, various reaction pathways (CO2 activation, epoxides activation and dual activation) are elucidated, followed by an in-depth analysis of both homogeneous and heterogeneous catalysts. Then, the paper evaluates the suitability of batch reactors, continuous flow reactors, and micro-pass reactors for this reaction. Finally, the paper highlights the importance of developing a green catalyst capable of selectively capturing low-concentration CO2 from industrial exhaust gas or air at room temperature and pressure, and converting it into cyclic carbonates in site. The insights presented in this paper offer a valuable framework and roadmap for future research endeavors in this field.