Covalent organic frameworks (COFs) have emerged as a thriving class of photocatalysts in various chemical transformations. However, the utilization of COFs as photoredox catalysts for atom transfer radical polymerization is rarely known. Herein, we designed and synthesized a series of phenazine-based functional 3D COFs with the dia topology. Structural regulation over interpenetration folds and energy levels of COFs was implemented through the substituent effects. These COFs can work as effective photoredox catalysts toward atom transfer radical polymerization. Notably, DADP-CF