Searching for highly efficient photocatalysts for water oxidation is the footstone for the development of overall water splitting systems and has been actively pursued. The construction of artificial Z-scheme heterojunction photocatalysts has been conclusively proven to be effective in boosting charge transport property and in improving the OER performance. Herein, Ag3PO4 particles anchored on modified crispy g-C3N4 flakes have been successfully fabricated. KOH-assisted surface modification of g-C3N4 flakes and intimate interfacial contact favor the accelerated charge transfer and highly improved OER efficiency. Ultrafast spectroscopy results reveal that modified g-C3N4 with crispy nanostructures possesses more trap-induced long-lived photogenerated holes, which are extremely helpful to combine with photo-generated electrons from the conduction band (CB) position of Ag3PO4 via the specific Z-scheme configuration, leaving more holes in the valence band (VB) of Ag3PO4 for the enhanced OER. Superb oxygen-evolving performance highlight the great promise of Z-scheme Ag3PO4-based heterojunctions in solar-driven photocatalytic water splitting.