Efficient separation of photogenerated electrons and holes is of key importance in photocatalysis. Tuning the charge separation pathway is significant but still suffering from low efficiency for the charge extraction from semiconductors. Herein, taking 2D g-C3 N4 (CN) nanosheets as a model photocatalyst, it was found the decoration of homophase junction between brookite TiO2 rods and nanoparticles (BN -BR ) onto CN can effectively modulate photogenerated charge extraction and transfer in BN -BR /CN composites. The BN -BR /CN exhibits a remarkably enhanced photocatalytic H2 evolution under visible light irradiation (λ>420 nm) compared with the single component. A continuous electron transfer channel constructed by an interfacial chemical bond Ti-O-N between CN and brookite rods (BR ) and BN -BR homophase junction between brookite nanoparticles and rods was proposed to benefit the charge extraction and transfer. This work provides a strategy to tune the charge separation and transfer to facilitate the photocatalytic performance in heterogeneous photocatalysis.