Metal-organic frameworks (MOFs) as a cocatalyst can enhance the photoelectrochemical (PEC) water oxidation performance to a certain extent, but still suffer from deficient exposure of active sites and low electron mobility. In this work, 2D Leaf-like zeolitic imidazolate frameworks (ZIF-L) were selected as a precursor for the generation of defective structures by tannic acid (TA) functionalization-assisted etching, and then coupling it with BiVO4 to prepare a novel and highly efficient TA@ZIF-L(Co)/BiVO4 photoanode by a simple impregnation method. The photocurrent density of TA@ZIF-L(Co)/BiVO4 composite photoanode achieves 4.21 mA cm−2 at 1.23 VRHE under AM 1.5 G illumination, which is superior to that of ZIF-L(Co)/BiVO4, and three times that of the bare BiVO4, with a charge injection efficiency of up to 80 %, and its stability is also remarkably improved. Experimental results and DFT calculations showed that the introduction of TA not only improved the light absorption efficiency, but also exposed more active sites, increased the electron density of the coordinatively unsaturated Co active sites, and enhanced the polarized electric field on the surface, thus accelerating electron mobility. This work demonstrates that TA as a surface modifier has great potential to activate metal sites and change the electronic environment of MOFs for BiVO4-based photoanode in PEC water oxidation, providing valuable insights into the rational design of photoanodes.