Electron donor-acceptor complexes are commonly employed to facilitate photoinduced radical-mediated organic reactions. However, achieving these photochemical processes with catalytic amounts of donors or acceptors can be challenging, especially when aiming to reduce catalyst loadings. Herein, we have unveiled a framework-based heterogenization approach that significantly enhances the photoredox activity of perylene diimide species in radical addition reactions with alkyl silicates by promoting faster and more efficient electron donor-acceptor complex formation. Besides offering broad substrate scope in alkene hydroalkylation, the newly developed heterogeneous photocatalysis substantially improves the catalyst turnover numbers in comparison to previous homogeneous photocatalytic systems and demonstrates outstanding catalyst recyclability. These research findings pave the way for the advancement of various efficient and practical organic transformations using framework-supported organocatalysts.