Photogenerated charge separation and transfer is one of the bottleneck steps in photocatalysis, and efficient charge separation strategies are strongly desired. Here, mimicking the electron transport chain in natural photosynthesis, we report the design and fabrication of a charge transfer chain using bismuth-based semiconductor as a proof-of-concept. In view of the thermodynamic energy band positions and structural similarity based on the density functional theory (DFT) analysis, heterostructured combination of α-Bi₂O₃, perovskite-like Bi₄Ti₃O₁₂, and sillenite Bi₁₂TiO₂₀ was designed for fabrication of charge transfer chain. By tuning the molar ratio of Bi and Ti precursors, the Bi₄Ti₃O₁₂ and Bi₁₂TiO₂₀ particles were formed on the surface of α-Bi₂O₃ by an in-situ transformation process, giving rise to Bi₁₂TiO₂₀-Bi₄Ti₃O₁₂/α-Bi₂O₃ composites with charge transfer chain. We propose that the effective charge transfer is accomplished among α-Bi₂O₃, Bi₁₂TiO₂₀, and Bi₄Ti₃O₁₂, which significantly improves the photogenerated charge separation and transfer, as indicated by photoluminescene, time-resolved photoluminescene, and electrochemical impedance spectra results. As expected, the Bi₁₂TiO₂₀-Bi₄Ti₃O₁₂/α-Bi₂O₃ shows the superior photocatalytic activity for the degradation of environmental pollutants with high concentration. Even for the refractory pollutants like 4-chlorophenol, the optimal Bi₁₂TiO₂₀-Bi₄Ti₃O₁₂/α-Bi₂O₃ composite shows 28 times higher than that of α-Bi₂O₃ for photocatalytic degradation, verifying the superiority of photogenerated charge transfer chain in photocatalysis. This work demonstrates the feasibility of the charge transfer chain strategy to boost the photogenerated charge separation, which is of great significance for designing energy and environmental-related materials in heterogonous photocatalysis.