Photocatalytic CO 2 reduction holds great promise for synchronously addressing carbon neutrality and producing fuels, although enhancing the photocatalyst activity and tuning the product selectivity remain enormous challenges. Herein, we synthesized four crystalline and porous benzothiadiazole-based covalent organic frameworks (COFs) with different carbonyl groups and reported a dual metalation strategy to fabricate Co and Ni dual-metal sites anchored on the benzothiadiazole-based COFs by the interaction between metal and thiadiazole for highperformance CO 2 photoreduction. Among the as-synthesized COFs metalated by Co/Ni dual sites, CoNi−COF-3 achieved an impressive CO generation rate of 2567 μmol g −1 h −1 with a selectivity of 92.2%, which were significantly higher than those of single sites. Experimental and theoretical results revealed that the superior photocatalytic performance was attributed to the synergic effect of the fully β-ketoenamine-tautomerized COF-3 configuration and dual-metal sites, which not only facilitated the photogenerated charge carrier dynamics but also reduced the energy barriers of *COOH formation and promoted CO 2 adsorption and CO desorption. This work provides valuable insights into the future design of improved COF photocatalysts for highperformance CO 2 conversion.

Conjugated polymers have emerged in recent years as prospective organic semiconductors in solar energy conversion. However, developing highly efficient conjugated polymers is still a grand challenge. Herein, we first demonstrate the fabrication of two donor−π–acceptor (D−π–A) conjugated polymers (N-DEA-TBP and L-DEA-DBP) by incorporating redox-active anthraquinone into pyrene units through acetenyl linkages. Comprehensive experiments and density functional theory calculations reveal that the network-conjugated chain and acetenyl-bridged conjugated structure facilitate charge utilization and separation/transfer in the skeleton. Such advantages of N-DEA-TBP endow it with outstanding activity for the photoreduction of CO2 in H2O without a sacrificial agent and photosensitizer, affording CO as the sole carbonaceous product with a generation rate of 70.25 μmol·g–1·h–1 and nearly 100% selectivity, which is almost 2.6-fold as high as that of L-DEA-DBP. Furthermore, N-DEA-TBP also exhibits an attractive photocatalytic performance for selective aerobic oxidation of sulfides under visible light irradiation. This study contributes new insights into their underlying structure and morphology for enhancing charge separation and transfer.