Covalent organic frameworks (COFs) are a new type of porous organic crystalline material, which have become an emerging platform for promoting the development of green energy technology due to their high surface area, adjustable pores, low skeleton density, and easy functionalization. In recent years, with the continuous advancement of synthesis technology, the synthesis efficiency and sustainability of COFs have been significantly improved, from traditional solvothermal methods to the emergence of various green synthesis strategies such as ion thermal, mechanochemical, and ultrasound assisted methods. This article reviews the main synthesis methods of COFs and explores their applications in the field of green energy, such as photocatalysis, gas adsorption and separation, electrocatalysis, battery, supercapacitor and Proton exchange membrane fuel cell. By analyzing the performance and mechanism of COFs in these applications in detail, this article further looks forward to the challenges and future development trends faced by COFs in green energy technology, aiming to provide valuable reference and inspiration for researchers in related fields.