AbstractThe design and synthesis of three-dimensional covalent organic frameworks (3D COFs) have still been considered as a big challenge. Here we report the design and synthesis of an AIEgen-based 3D COF (3D-TPE-COF), with a high surface area (1084 m² g⁻¹). According to powder X-ray diffraction and continuous rotation electron diffraction analyses, 3D-TPE-COF is identified to adopt a seven-fold interpenetrated pts topology. Interestingly, 3D-TPE-COF emits yellow fluorescence upon excitation, with a photoluminescence quantum yield of 20%. Moreover, by simply coating 3D-TPE-COF onto a commercial blue light-emitting diode (LED), a prototype white LED (WLED) under continuously driving without degradation for 1200 h was demonstrated. The present work suggests the possibility of using COF materials for stable WLEDs, which will greatly inspire us to design and synthesize fluorescent 3D COFs and facilitate the development of COF-based WLEDs in future.