Covalent organic frameworks (COFs) are crystalline and porous organic materials attractive for photocatalysis applications due to their structural versatility and tunable optical and electronic properties. The use of photocatalysts (PCs) for polymerizations enables the preparation of well-defined polymeric materials under mild reaction conditions. Herein, we report two porphyrin-based donor-acceptor COFs that are effective heterogeneous PCs for photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT). Using density functional theory (DFT) calculations, we designed porphyrin COFs with strong donor-acceptor characteristics and delocalized conduction bands. The COFs were effective PCs for PET-RAFT, successfully polymerizing a variety of monomers in both organic and aqueous media using visible light (λ max from 460 to 635 nm) to produce polymers with tunable molecular weights (MWs), low molecular weight dispersity, and good chain-end fidelity. The heterogeneous COF PCs could also be reused for PET-RAFT polymerization at least 5 times without losing photocatalytic performance. This work demonstrates porphyrin-based COFs that are effective catalysts for photo-RDRP and establishes design principles for the development of highly active COF PCs for a variety of applications.