Covalent organic frameworks (COFs) have gained considerable attention due to their design possibilities as the molecular organic building blocks that can stack in an atomically precise spatial arrangement. Since the inception of COFs in 2005, there has been a continuous expansion in the product range of COFs and their derivatives. This expansion has led to the evolution of three-dimensional structures and various synthetic routes, propelling the field towards large-scale preparation of COFs and their derivatives. This review will offer a holistic analysis and comparison of the spatial structure and synthesis techniques of COFs and their derivatives. The conventional methods of COF synthesis (i.e., ultrasonic chemical, microwave, and solvothermal) are discussed alongside the synthesis strategies of new COFs and their derivatives. Furthermore, the applications of COFs and their derived materials are demonstrated in air, water, and soil pollution management such as gas capture, catalytic conversion, adsorption, and pollutant removal. Finally, this review highlights the current challenges and prospects for large-scale preparation and application of new COFs and the derived materials. In line with the United Nations Sustainable Development Goals (SDGs) and the needs of digital-enabled technologies (AI and machine learning), this review will encompass the future technical trends for COFs in environmental pollution control.